TWI270920B - High-performance ozone water cleaning system for semiconductor wafer, and method thereof - Google Patents

Abstract

This invention relates to high-performance ozone water cleaning system for semiconductor wafer, and a method thereof. The method mainly utilizes ultra-pure water and gas-phase ozone, a gas-liquid dissolving combination process in a mechanism environment with gravity field. The manufacturing process employs the information feedback control technique of cleaning solution concentration dynamic analysis, and cleaning solution. It includes high concentration large flow rate liquid phase ozone water, a dynamic monitor of ozone, additive concentrations, and water temperature in solution during wafer cleaning, and a monitor value analysis feedback and reaction for performing an adjustment control operation to carry out continuous, fast, mass wafer cleaning under consistent effective wafer surface cleaning capability. The system comprises a liquid-phase ozone generator, a storage tank or a cleaning tank, an additive supply mechanism, a monitor mechanism, an automatic feedback, and a control mechanism.

Description

1270920 §93117037 _Ά 曰Revision 5, invention description (1) Technical Field of the Invention The present invention relates to a system and method for high-performance ozone water cleaning of a semiconductor wafer, which relates to ozone cleaning of a semiconductor wafer. The technical field, in particular, refers to an ozone aqueous solution which utilizes gas phase ozone and water solvent in a high mass transfer in a mechanism and dissolves in a liquid phase to form a cleaning solution, and ozone oxidizes the surface of the wafer material, and cooperates with the ozone cleaning process in the cleaning process. The cleaning solution concentration monitoring and concentration feedback control are maintained, and the ozone cleaning method and device for oxidative decomposition cleaning of the wafer and the glass substrate surface photoresist or other organic deposits can be quickly and effectively performed. [Prior Art] According to the fabrication of semiconductor wafers, each step included in the process: etching, oxidation, deposition, photoresist removal, and chemical mechanical polishing are all sources of wafer surface contamination, and wafers. Surface contamination has always been the biggest obstacle to process quality and production. Therefore, it is necessary to repeat several cleaning processes in the wafer process. With the development of ultra-large integrated circuits (VLSI, ULSI), wafer cleanliness requirements are becoming more stringent. The purpose of cleaning the surface of the wafer is to remove all trace contaminants, including organic matter, metal deposits, particles, etc., and to control the wafer surface, form a thin oxide film (T hi η ο X ide ), and maintain the wafer. The surface is flat and resistant to water and electricity. The clean methods currently known and often used can be broadly classified into wet and dry methods. Among them, the dry cleaning method uses a chemical reaction generated by high energy (such as heat, electric energy, and radioactivity) to perform surface cleaning treatment. In addition, the wet method utilizes a solvent, an acidic solution, a surfactant, and a mixture.

Page 5 1270920 Case No. 93117037 修正 Amendment V. Description of the invention (2) Washing, oxidation, etching and dissolution of pure water; this is also the most commonly used cleaning method. As for wet cleaning technology, it is currently widely used by the industry, including the following methods: 1· H2S04/H 20 2 @100 ～130°c (SPM), also known as n Pr ianha C 1 ea η ”, to remove organic Contaminant 2.HF or diluted HF (DHF) @20~25°C, the main purpose is to infiltrate the oxide film (Silicon ozide) 0 3·ΝΗ40Η/Η 20 2/Η20 @30 ～80°C (APM), It is used for alkaline water and invading the surface of insects to remove fine particles. At the same time, it can remove organic and metal-contaminated dyes. 5. Genus, and standard cleaning method, the surface of the round surface is clean • According to the fruit of the round factory, the same strong acid dust Indoor HCl / H2 〇 2 / H2 〇 @ 65 ~ 8 5 ° C (HPM), mainly used to remove metal stains H2S0 4 / 0 3 / H20 @ 90 ~ 120t (S0M), can remove organic matter, gold to reduce the amount of H2S0. 'The current RCA Standard Clean is often used in the cleaning process of the previous wafer process, which is to integrate the above-mentioned wafer 4 for wafer cleaning; the above cleaning methods, for crystalline organic photoresist and others The removal of solid contaminants can achieve a high 2 effect, but in the cleaning process, the aforementioned RCA wafer cleaning Chengmen also estimated that it is necessary to use ultra-pure water of 45,000 tons (equivalent to ten eight daily water consumption) per day, and use H2S () 4, HmH (four) agents when the effect is high. It will produce hundreds of strong inspection waste liquids (harmful waste sinus I, , , , , ^ fruit) emissions. Some of the shortcomings of the court often cause the air (Fab) air and exhaust gas treatment, every wind..., psychological system burden And the chemicals are in

Page 6 1270920 θ Correction Case No. 93117037 V. Description of invention (3) The volatility at high temperatures reduces the net effect of the concentration of clean liquid. Do not make 'Keep it clean', 'Processing Nano" and "Green Production 3 & The common trend of high-tech industry development, including the second and the future LCD, melon, communication components, ultra-precision processing, win Rice, TFT-electronic components and other technologies are all actively moving towards ultra-fine 盥 ultra-clean = making, nano in the nano-process environment, 'very small amount of pollution in any part of the process = research and development 'granules, metal ions, organic impurities, etc.) The existence, ^ things (such as micro-particles: great damage, and this strict process cleanliness needs to be provided by the RCA cleaning program of the traditional electronic process, and '... method resources consumption, high pollution water discharge The process will also be a serious fan of the high water sub-industry development. In particular, "Environmentally Benign Manufacturing, ^ , . « The latest trend in the future development of the photovoltaic industry process, the second process of the new process = Force is to pursue the same or better implementation of the current technology (Pr〇cess Performance), while at the same time the environment is cleaner and more friendly. To make up for the lack of traditional cleaning methods, at the same time can achieve at least The cleansing effect has been gradually washed by ozone instead of other chemicals in the past ten years. The odor f is a strong oxidizing gas, an unstable gas, and has a strong residual property such as a double sulphur, such as cerium oxide. (MnO 2), so that it can quickly destroy B, so it can not only reduce the cleaning step, but also reduce the negative impact on the safety of the cleaning system. The ozone water used for wafer washing needs to have the following technical characteristics: ) door 'name clarity · on-site manufacturing, no storage and transportation

1270920 _ Case No. 93117037_Yearly 曰 Amendment _ V. Invention Description (4) Pollution problem, and can replace the Η 20 2 used in the cleaning process to avoid metal contamination concerns. (2) High process efficiency: It can produce high-purity ultra-thin (<2〇A) gate oxide, which is superior to the current thermal oxidation process performance and is required for the 0.13/m process. (3) Low-pollution emissions··Can replace the H 2S0 4, HC 1 and Η 20 thin chemicals used in the RCA wafer cleaning process to reduce the waste of waste acid (hazardous waste) and save cleaning. The process uses ultra-pure water up to 20%. • Therefore, the use of ozone water cleaning, considered as one of the most promising new generation IC process technologies, can be applied to UPW micro T0C reduction, photoresist removal, post-etch cleaning, post-CMP cleaning, pre-gate Cleaning and ultra-thin gate oxide growth and other processes. At present, ozone production methods, including photochemical methods, are used in applications where a small amount of ozone is produced. The discharge method is a phenomenon similar to the electric shock in nature, so the humidity of the air is very high. And the so-called plasma method, which uses an aluminum vacuum tube containing an blunt gas to generate an electron impact at high energy to produce ozone. As for the ozone cleaning produced by the above method, it is necessary to dissolve the gas phase ozone in pure water to form a clean solution for cleaning operation, and is different from the low concentration ozone required by the conventional industry (丨ppm). From within to a few ppm), semiconductor and optoelectronic cleaning processes require long-term stable supply of medium to high concentration ozone water (tens of ppra range), so the solubility of /gas phase ozone water is one for the production of ozone-containing ultra-clean cleaning solution.

Page 8 1270920 _ Case No. 93117037 Year __ V. Invention Description (5) The important bottleneck of the ring. Moreover, the solubility of gas phase ozone is low, and it is extremely sensitive to environmental changes; and the main factors affecting the solubility of gas phase ozone water include gas phase ozone concentration, solution temperature and acidity. The current technology attempts to control the physical conditions to bring the thermodynamic saturation concentration closer to the solubility of the ozone in the South. The relevant technical data and patent publication results, such as in the ozone water production system, there are US 5,9 7 1 , 3 6 8 (ozone water generation system design, increased solubility with pressurized vessel) and DE19752769 (ozone water production system design, to pipeiine

_ line 0 ) solution). In the design of wafer cleaning system, there are u S 5,7 7 6,2 9 6 , US 5,4 6 4,4 8 0 (low temperature 1~1 5 °C) immersion ozone water wafer cleaning tank), DE1 9 8 0 1 3 6 0 (rotary ozone water wafer cleaning tank, operating temperature 2 〇 ~ 70 ° C) and JP2 0 0 0 0 584 96 C high temperature ozone water wafer cleaning system). In the design of wafer cleaning formulations, there are US6, 080, 53 1 [organic c c removal of metal oxide layer with D 1-0 3 (about 36ppm)], 1^5,964,953 [to 01-03 (several? ?111) with the leg 4011 (89), removed

Al,organics], US5,759,971 (0 is dissolved in 0·03 to 0.05% HF, used as wafer cleaning solution), 1^5, 6 32, 847 [0 箨 (11 (: 1 + heart) (3 (1). Clean the wafer surface in Nibble type], US5,62 6,68, EP0 7 0848 0 [D I-0 3 (several ppm) + HF (aci) with brush- scrubbing, clean polished Wafer, reduce microroughness] and FR2779980 [mix 0 3 into 11 (: 1 (39) and then mix with 117 (called), used as wafer cleaning solution]. Analyze the patent content of the aforementioned research on ozone water cleaning solution,

Page 9 1270920 曰修" _ Case No. 93116037 V. Description of the invention (6) More than = good 2 oxygen water gas-liquid contact system, and the cleaning system 1 to increase the ozone water concentration and increase the reaction rate purpose = f 3 | 0 I Μ Λ心,,············································································ One of the reasons why the daily research and development of the 3 rounds of the month is more concentrated. However, it has not been able to be popularized in the process so far. Because of the above-mentioned patents, the application of the patents to the wafers is not possible, and the ozone concentration distribution in the cleaning tank cannot be grasped. The wafer cleaning is mainly performed by ancient and smelly milk. The private sequence is used in the semiconductor process to disperse the ozone gas into two ozone to disperse the agitation or aeration, thereby improving the mass transfer effect, so as to increase the gas-liquid contact surface, which cannot effectively provide rapid mass transfer and still be subjected to gravity and buoyancy. Limit 'liquid phase ozone water. t wafer fruit and pure water phase dissolve, forming a high concentration of ozone, and in the helmet method C tank 'f rapid consumption of cleaning solution can be automatically adjusted: makeup ί ^ tank ozone concentration distribution or i ozone Insufficient concentration, helmets: two often lead to dissolution in the middle and late stages of the reaction process, or other oxide layers are effective to remove the organic matter on the surface of the wafer (such as light can not increase the yield. Bearing 'must extend the wafer cleaning time, and then industry. Although there are some parts of the method to perform a large number of continuous cleaning processes for oxidizing, but the beans promote good procedures, by irradiating UV light to increase the concentration of ozone, and not only the degree of A, ▲ still depends mainly on the aqueous solution. The ozone can not only improve the oxidation energy without the irradiation of UV light.

1270920 Case No. 93116037 Month 修正 Amendment V. Description of invention (7) Force; in the currently known gas phase ozone and pure water dissolution technology, effective breakthroughs are still not available. SUMMARY OF THE INVENTION One of the main objects of the present invention is to provide a method for cleaning semiconductor wafers with high-efficiency ozone water, mainly by using liquid phase ozone formed by dissolving gas phase ozone in a high liquid phase, and achieving wafer by ozone oxidation. And the method of clean cleaning the surface of the glass substrate, which can quickly and effectively oxidize and decompose the photoresist or other organic deposits on the surface of the wafer.

• Another main object of the present invention is to provide a high-performance ozone water cleaning semiconductor wafer method capable of monitoring and feedback control operation adjustment in response to changes in ozone concentration in the cleaning solution in the cleaning process, and stably maintaining the cleaning process. The conditions and application parameters improve the operation speed of the semiconductor process and reduce the complexity and cleaning time of the traditional wafer cleaning method.

Another main object of the present invention is to provide a method for high-efficiency ozone water cleaning of a semiconductor wafer, which utilizes a simultaneous ozone concentration measurement and feed control reaction of the cleaning solution, and can quickly and efficiently process a large number of wafers in a continuous manner. Maintain or even control the oxidative decomposition capability of the program to achieve effective and precise control of the characteristics of the oxygen O on the wafer surface to meet the requirements of different wafer surface cleanliness. A further main object of the present invention is to provide a method for cleaning semiconductor wafers with high-efficiency ozone water, which utilizes ozone with good oxidizing ability and uses hydrogen peroxide as an additive to obtain a wafer cleaning solution which is less likely to remain and is less toxic, compared to It is customary to use concentrated sulfuric acid or other more harmful agents.

Page 11 1270920 _ Case No. 93117037_年月日日__ V. Description of invention (8) To reduce the environmental problems caused by the extensive use of chemical agents with environmental impacts, resulting in chemical disposal and disposal. According to the present invention, the system for cleaning ozone semiconductors in the south of the ozone-enhanced water system comprises: a liquid phase ozone generating mechanism; and the ultrapure water and the gas phase ozone provided by the mechanism in accordance with the gravity field operation High quality transfer contact dissolution to obtain high ozone liquid phase dissolution cleaning solution; a storage tank or cleaning tank to provide storage of the above aqueous solution for cleaning, and a working space for providing wafer cleaning; ® an additive supply mechanism Under the control of an automatic control mechanism, the mechanism for putting the additive into the storage tank or the cleaning tank; a monitoring mechanism, including liquid odor concentration, additive concentration, pH control and water temperature control monitoring, at any time During the cleaning process, the optimal set value of various parameters in the monitoring solution is maintained, and the detection result feedback type is sent to an automatic feed control mechanism for analysis and reaction through the transmission technology; an automatic feed control mechanism receives the aforementioned monitoring mechanism at any time. Feed back various concentrations and conditional parameter detection data, and analyze and set value comparison, and then reaction concentration, water temperature and pH value Parameters, and to adjust the parameters and conditions of maintaining effective control of the cleaning set. In a preferred embodiment, the liquid phase ozone generating mechanism is a high-speed centrifugal gravity rotating packed bed, and the high-efficiency separating device is operated by the supergravity technology to enhance the quality of the gas phase ozone and the ultrapure water. The contact and dissolution effects are transmitted to form a high concentration of ozone water dissolved in the high liquid phase as a cleaning solution. And can use the gravity field adjustment of the mechanism to control ozone and water solvent

Page 12 1270920 Case No. 93117037

5. Inventive Note (9) The forced solubility between (9) is used to maintain the strong sound of the cleaning solution. Different from X 3 In another preferred embodiment, the cleaning operation uses hydrogen peroxide (H 2 〇 2, hydrogen peroxide), which can improve the oxidative decomposition ability of the organic compound. A Japanese yen surface implementation method] The invention is related to the use of a high concentration of large flow rate to form a liquid phase odor chlorine water helmet, the main, also, -, and six 4 oxygen water production system, the wafer ϋ π : in the storage tank or cleaning degree and conditions, at the same time in the cleaning process, through the liquid-soluble concentration parameters such as ozone; branching 'caps to clean the tank inside the various measurements' and use, acid test and water temperature, etc. The monitoring of the environmental conditions enables the feedback control of the number of the technical soils to be automatically adjusted, and the optimum concentration distribution effect of the first groove in the wafer table is automatically adjusted, and remains effective.

The present invention performs continuous rapid mass wafer cleaning. The main technical content of the preferred embodiment of the high-performance ozone water cleaning semi-conductive embodiment is appropriately disclosed in the following examples of the preferred embodiment of the present invention. The main I of the present invention is appropriately implemented. The semiconductor wafer pattern is a flow chart and an architectural diagram of a high-performance odor-free operation of a high-performance ozone water cleaning according to a preferred embodiment of the present invention. The preferred embodiment of the present invention consists of a liquid phase odor=shuiqing1 semiconductor wafer system, which is mainly composed of an ozone water-solubilizing mechanism 1 for providing a gas phase ozone and ultrapure water dissolution 'month tank 2 for storage. Ozone water and crystal

Page 13 1270920 Amendment 931 93117037 V. Invention Description (10) Round immersion cleaning operation; an additive supply mechanism 3, providing supply and supply speed control of the additive; a monitoring mechanism 4, = process > monthly washing process The application springs for monitoring the concentration and environmental conditions at any time are collected from the feedback control mechanism 5, and the value-added knife-ratio pairs fed back by the monitoring mechanism 4 are collected, and the instantaneous response control concentration adjustment operation is composed. Line = liquid phase ozone generating mechanism i, mainly in the provision of gas phase ozone, medium, ^ Ϊ, gluten solution to form a concentration of ozone water generation mechanism; as shown in Figure 2 and Ϊ t = shows: in a specific embodiment, the liquid Phase ozone generating mechanism ^Fig. Centrifugal gravity field device has a centrifugal gravity field ring which is generated in the main body shell u - the ancient gravity tube; in fact, a droplet or mist condition is formed, and then the reverse direction is transmitted. The gas phase odor* is as follows: solution, stirring and mixing, i rapidly dissolving the gas phase ozone: to obtain a high concentration liquid phase ozone aqueous solution. In the structure of the embodiment of the negative transfer machine, the liquid phase ozone generating mechanism 1 is used in a packed bed configuration to provide dissolution in the packed bed; and in the '曰ίϊϊ environment' 16 liquid ultrapure water and The gas phase ozone is highly decomposed into ozone water as the wafer cleaning solution of the present invention. For example, as shown in Fig. 3, in the concrete implementation 12, the gas and liquid dissolve operation; a rotating body 1 in the main body casing 1 with a gas seal shaft, and the rotating body 1 3 Rotating the gear plate ΐ3ΐ; a power member 14 for driving the rotating body 13 ,, such as a motor configuration; an ultrapure water spray, placed in the center of the shaft portion of the rotating body 丨3, and introduced with ultrapure water 14 pages 1270920 _ case number 93117037 曰 five, invention description (11) mouth 1 6 phase connection, as the introduction of ultrapure water operation; - ozone gas introduction port 17, for connection; oxygen; = into the spray! The introduction of 虱 臭 巩 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The ozone gas concentration parameter introduced by the analysis and analysis is detected when the ozone is generated. In addition, in the operation, the water inlets, the water outlets, the phases of the ozone gas in and out of the generating mechanism 1, or the related fine gas pipes are all connected, and the commonly used airtight members are matched [all are omitted] Specifically, the body of the liquid phase ozone generating mechanism 1 is rotated, and in the legendary structure, the system is stacked as shown in FIG. 5 and includes a carcass, such as a fourth body. The outer wall 111, the crucible is also blocked by the colony, and is defined as the inner wall 112 of the rotation. = J material barrier mesh is defined by one of the rotary ingots or other dispersible two Hungarian porcelain fillers, metal oxides. The body of the packed bed during rapid rotation: strong; U material structure. In order to maintain the height 113, such as a screw, the material of the liquid phase odor and the material of the red body and the rotating inner wall 112 of the rotating body is fixed, and the material source of the material is used. Mixing and dissolving to produce ozone water; one oxygen preparation: continuous, and pure water supply unit 61, providing ultra-pure water phase ozone generator; t 2' for generating and providing ozone input to liquid speed centrifugal ίί Γ And in the liquid phase ozone generating mechanism 1 with high-power red turning operation, the residence time of gas and liquid contact can be increased, page 12, 1270920 _ case number 93171037 玍. . Amendment---- -----月__«__^----- ~ --- V. Description of invention (12) and change the micro-gravity environment of the gas and liquid interface, while passing through the liquid phase ozone generating mechanism 1 A large increase in the mass transfer area of gas and liquid contact can effectively improve the solubility of ozone in aqueous solution and reduce the time required for mass transfer of ozone to equilibrium liquid phase ozone concentration, which can be adjusted by the rotational speed of the power component 丨4. The gravity field in the liquid phase ozone generating mechanism 1 is changed; the high-concentration ozone aqueous solution generated by the liquid phase ozone generating mechanism 1 is sent to the cleaning tank 2 through the connecting line. a cleaning tank 2, mainly for providing ozone water storage of the cleaning solution generated by the liquid phase ozone generating mechanism, and the fish smashes the space; the cleaning 352 is in the body of the body, and the cleaning operation container is Through the pipeline and the liquid phase odor,, ° ° 疋f with a tube, knot, to obtain ozone water after the cleaning: = ozone water, then a vent 2 2 odor water. In use, the ultrapure water inlet port 16 is used to return, force or return it to the system. The additive supply mechanism 3 is used by the dry source. A monitoring mechanism 4, mainly for wafers in production, for monitoring the cleaning solution at any time #θθ 2 for cleaning process, the parameter of the liquid phase ozone concentration detecting unit 4; the mechanism element 42, the pH value product The control unit 43 and the water temperature price and the additive concentration detection single concentration detecting unit 4 are disposed in the cleaning tank 2 ι early 70 44. The liquid phase ozone enthalpy is coupled in the detection cleaning tank 2 for the addition of the t-additive additive used in the embodiment of the present invention directly to the controlled & After adding as the best, you can increase the wafer table J = to hydrogen peroxide (H2 〇 2) I. Oxidative decomposition energy of organic matter

1270920 ---- Case j 93117037, invention description (13) _ self, 丨 "Use liquid water odor concentration, and in the specific embodiment configuration, production eight, phase odor analyzer use, can be carried out The liquid phase ozone is taken as follows: the second concentration is the additive concentration unit 42, which is also in the cleaning 枰; ^ 农佶Ϊ ί: Is the concentration of the additive within the set value range? f value is ΐ43, Using the ρ Η value detector "I in the cleaning tank 2 acid-base === by the controller 432 to carry out the data signal ^, field i unit 44, at any time to measure the temperature of the solution, and 隹 ^, ;! , 5 will be: Ϊ monitoring agency 4 of various detection or measurement results data 2: • reaction control transport to an automatic feed control mechanism 5, for analysis and comparison

5 control units: with: software... The setting of the standard value and the record of the second feed / section, with the collection of various concentrations or temperature standards, and;:; the automatic feed control mechanism 5 to detect and return the funds Standard, d; 疋: comparison, while controlling the results. Order response and output control signals for institutional operation

The apple feed control mechanism 5 is configured in a preferred embodiment; the network learns: control or hardening parameter control or class deviation; 2 =, mainly to quickly respond and reduce the aforementioned automatic c is the adjustment of the parameters. The oxygen concentration detecting unit mechanism 5 obtains the liquid phase odor of the monitoring mechanism 4:::1 fruit pair: blue tr...water washing solution... conditions such as setting the beam quasi-comparison/knife-analysis Round cleaning process", value, and then adjust the liquid phase ozone generating mechanism 1

1270920

The rotational speed of the force member 14 and the voltage value of the ozone generator 62 or the flow rate of the pure water supplier 61 are used to introduce ozone water having a set concentration into the cleaning tank 2. Or, according to the additive concentration data of the detection feedback, the amount and speed of the additive supply mechanism 3 are reacted and controlled. According to the foregoing preferred embodiment of the present invention, a high-performance ozone water cleaning semiconductor wafer system, in the method of using the system for wafer cleaning, please refer to one of the inventions shown in FIG. The operational flow chart and architectural flow chart of the method for the high performance ozone water clearing 2 semiconductor wafer of the preferred embodiment. Blind first, liquid phase ozone generating mechanism 1 operates to produce liquid phase ozone water clear T solution;;: P uses the high gravity rotating packed bed to provide contact surface area and change contact for improving gas phase odor rolling and liquid ultrapure water The ring production conditions at the time of mass transfer are combined with the high concentration of ozone and water to form a high concentration of ozone and water. In the specific operation process, the pure water supply unit 6 1 'superior The pure water is introduced into the liquid phase ozone generating mechanism by the ultrapure water introduction port, and is sprayed toward the rotating body 13 by the ultrapure water jet 丨5, and is driven by the rotating body 13 to be rotated by the rotating member ,4. The centrifugal force is extracted outward from the filler shutter 131. The rotating body 131 and the pure water inlet port 16 are bypassed by gas pressure, and are sealed by a gas-tight shaft seal to ensure the airtightness and pressure maintenance of the rotating packed bed, and the pressure change is also 2 . The pressure gauge or direct observation by a differential pressure display. The odor and oxygen are generated by the second generator 62, and are connected to the liquid-phase ozone generating mechanism via the pipeline, and the oxygen inlet port 17 is input into the high-gravity rotating packed bed, and the liquid-phase ozone is generated from the liquid phase. According to the direction of the material, ozone gas and ultrapure water enter and feed, which adopts the reverse flow of mass transfer, and ultrapure water is generated by liquid phase ozone.

1270920 amendment

Charm 93117037 V. Invention Description (15) Ultra-pure water inlet at the top of the organization 1 ^ Channel 18 Outflow for easy use. On the ozone f, the side ozone gas inlet 17 from the bottom ozone aqueous solution leads: 1:==Generation mechanism [mandatory gas liquid quality #, residual ozone body: bed" main body η inside the top of the gas pressure bypass 19 release The liquid phase ozone generating mechanism can effectively promote the * m by the high-speed rotation of the liquid phase ozone generator and the forced surface contact machine t, which can effectively generate the mixing and mixing (4), and the rapid phase 6. Oxygen: Through this - mass transfer mechanism 'effectively and quickly dissolve the ozone in the water solvent, the present invention is suitable for the wafer clear main liquid outlet 18 to be discharged and transported to the cleaning tank 2 for storage. At the same time, the additive is also activated for the hiring device 3, according to the set optimal concentration ratio of additives such as hydrogen peroxide (H2 〇 2), added to the aforementioned cleaning tank 2, mixed with ozone water to form a cleaning solution, and The wafer to be cleaned is immersed in the cleaning preparation 2, and the mixed solution of the odor, the water and the additive is used for the oxidative decomposition cleaning of the surface of the crystal. In the process of immersing the wafer in the cleaning tank 2 for cleaning, the detecting units 4, 42, 43, and 44 of the monitoring mechanism 4 of the system of the present invention simultaneously start detecting various application parameters at any time; The ozone concentration debt measuring unit 41 samples and scores the debt concentration of the ozone concentration in the solution in the cleaning tank 2

1270920 Case No. 93,171,037 Revision 5, Invention Description (16) Analysis; additive concentration detecting unit 4 2, also sampling and analyzing the concentration of the additive in the cleaning tank 2; the pH value detecting unit 43 is cleaning The measurement of the pH value is performed in the tank 2; and the water temperature detecting unit 44 measures the temperature of the solution at any time, and instantly detects various parameters in the solution and the cleaning tank 2, and detects the acquired data. The automatic feed control mechanism 5 of the system of the present invention is fed back to analyze and compare the parameters.

The automatic feed control mechanism 5 in the system of the present invention also collects and analyzes the parameters detected by the monitoring mechanism 4, compares the set standard values, and makes a rapid reaction to the comparison results.眷, and then quickly adjust various operating parameters, such as the concentration of gas phase ozone generated by the liquid phase ozone generating mechanism 1, and the ratio of the rotational speed to the gas-liquid feed ratio, the amount of hydrogen peroxide additive, the pH value, and the water temperature, so that the cleaning tank The cleaning solution in 2 can maintain a stable liquid phase ozone concentration, additive concentration, pH value and water temperature, etc. It is in the best wafer cleaning conditions, can withstand a large amount of wafer cleaning load in an instant, and respond quickly And stably maintain the liquid phase ozone concentration in the cleaning tank, improve the wafer cleaning efficiency and reduce the power consumption, and reduce the use of chemical cleaning drugs, which can also reduce the impact on the environment when the semiconductor plant operates, and reduce the water consumption.

According to the foregoing method of the present invention, a P method for cleaning a semiconductor wafer with high-efficiency ozone water is carried out. It can obtain high concentration and high solubility gas and liquid dissolved ozone aqueous solution, which can be used for wafer cleaning, and can obtain excellent fast and effective oxidative decomposition of photoresist or other organic deposits on the wafer surface; Monitoring and feedback control of solution concentration during cleaning, compared with the conventional ozone water cleaning method, there is no wafer immersion and rapid consumption of the cleaning solution.

Page 20 1270920 Case No. 93116037 Issue 5, Invention Description (17) Ozone, resulting in insufficient ozone concentration in the solution in the middle and late stages of the reaction, can not effectively remove organic matter (such as photoresist) or other oxide layer on the surface of the wafer In addition to the problem, the present invention can additionally control the detection and feedback of various application parameters and content concentrations of the solution in the cleaning tank 2 through the cleaning process, especially to maintain the ozone concentration continuously. Wafer cleaning oxidative decomposition capability 'maintains the most efficient removal of organic matter (such as photoresist) or other oxide layers on the wafer surface, and can be used to clean wafers in large quantities and continuously.

In another preferred embodiment, the liquid phase ozone generation in the present invention generates liquid phase ozone water, and the wafer can be used in the cleaning process of the cleaning tank 2, and can also be combined with short-wavelength ultraviolet light (UV). The irradiation further improves the oxidative decomposition rate of the organic matter in the cleaning process, and can fully utilize the ozone and hydrogen peroxide dissolved in the ultrapure water to effectively perform the non-circulating cleaning process, and the residual ozone and hydrogen peroxide pair The impact of the environment is minimized.

The present invention provides a system for high performance ozone water cleaning of semiconductor wafers and methods thereof, and it is to be understood that the embodiments disclosed herein are intended to be illustrative and not to limit the scope of the invention. Other embodiments and applications described are considered to be within the scope of the invention. It is also necessary to know for sure that although the specific implementation of the system and method for high-performance ozone water cleaning of the punched conductor wafer has been discussed, these implementation structures that perform most of the similar functions are still patents for the present invention. Within the scope of the scope to be protected.

Page 21 1270920 _ Case No. 93117037_Yearly revision __ V. Description of invention (18) [Symbol] 1 liquid phase ozone generating mechanism; 2 cleaning tank; 3 additive supply mechanism; 4 monitoring mechanism; Control mechanism; 10 gas phase odor analysis unit; 1 1 main body casing; 1 2 gas-sealed shaft; 1 3 rotating body; 1 4 power components; 1 5 ultra-pure water nozzle; 1 6 ultra-pure water inlet; 7 ozone gas inlet; 1 8 ozone water outlet; I 9 gas pressure bypass; 20 0 discharge port; 4 1 liquid phase ozone concentration detection unit; 4 2 additive concentration detection unit; 43 pH value detection unit ; 44 water temperature detection unit; # 6 1 pure water supply; 6 2 ozone generator; 111 rotating outer wall; 11 2 rotating inner wall; II 3 supporting fixed member; 43 1 pH detector; 432 pH Controller.

Page 22 1270920 _ Case No. 93117037_Yearly Revision _ BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a system cleaning method according to a preferred embodiment of the present invention; FIG. 2 is a system architecture of a preferred embodiment of the present invention Figure 3 is a structural view of a liquid phase ozone generating mechanism of the present invention; Figure 4 is a structural view of a rotating body in the liquid phase ozone generating mechanism of the present invention; and Figure 5 is a rotating body of the liquid phase ozone generating mechanism of the present invention. Side view.

Page 23

Claims (1)

1270920 丄---^^,931170^7 ',, apply for patent scope I cooperate! Performance ozone | Contains: ¥ 曰曰 51 for continuous 古 field ancient ί phase ozone generator = shell transfer contact dissolution environment l · first solution ; cleaning tank, pipeline connection | solution and storage, and provide the addition of crystal additive supply mechanism; a monitoring mechanism, layout | detection of cleaning solution various I should control the mechanism; an automatic feed control mechanism, control agency detection, ratio For the design, and then the decomposition can be other deuteration and accept the above-mentioned monitoring and collection | rapid reactor | liquid with the best oxygen I (such as photoresist) or ® cleaning wafer 2. If applying for a conductor wafer I Additives Mixing Group 3. If the scope of application is patented, the scope of the solution of the solution is /! 曰Revised water clearing = semiconductor wafer system, which is used for large-scale cleaning system, the system architecture is 'super pure Gravity of water and gas phase ozone to obtain high ozone liquid phase dissolved wafers. The liquid phase ozone generating mechanism obtains a space for cleaning round immersion in the cleaning; and the aforementioned cleaning tank is connected, and the controlled addition is performed. In the washing tank, the parameters are used in the cleaning process, and the data is fed back to an automatic feed input and the solution application parameter setting value is memorized; the various parameter data of the feedback feed are measured, and the standard value is instantly set, and the comparison result is quickly made. Adjusting the operating parameters to maintain the solvent's ability to maintain the most effective removal of the organic layer on the wafer surface, and to clean the wafer cleaning solution with a large number of high-performance ozone water as described in item 1. Ozone water is used and used. High-performance ozone water cleaning half described in item 2 Page 24 1270920 t No. VI. Patent scope The conductor wafer system is controlled by flow and liquid speed. 4. If you apply for a miscellaneous wafer, you can do it in the process of cleaning. For example, if you apply for a wafer, you should use the material: system/ozone generation. 6. If you apply for a wafer, modify the system. Separate gravity swirling fluorine phase ozone and high concentration of sacrificial 7 · If applying for the fast centrifugal gravity of the Wei wafer, to control the concentration of ozone waves or suitable 8 · If applying for the introduction of miscellaneous wafers, the odor analysis Monolithic, in which the patent range of phase ozone is unified, one step is combined with the patent scope of organic matter, which is connected with a super device, which is used for the patent scope, in which the ozone water of the ultra-pure water is filled. The patent scope is the same, in which the field is based on a different range of patents for water solvent, where the concentration of the ozone water is used to supply the ultrapure water and the second item of the liquid phase ozone generating mechanism. The high-efficiency ozone water cleaning method described above is the oxidative decomposition rate of the ozone water in the liquid phase ozone generating machine, the gentleman's short-wavelength ultraviolet light (four). ^ High-performance ozone water cleaning half as described in item 1. The liquid phase ozone generating mechanism is used to produce a pure ozone water supply device to obtain ultrapure water introduction, and to extract gas phase ozone. : The high-efficiency ozone water cleaning of the four phases is used for half-time use, and the high-liquid phase is used to contact the high-liquid phase. The scent of the scented water is cleaned by a singer, and the height of the power component is changed from the power component to the % amp amp % % ) ) ) ) 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制 强制To maintain the water-washing solution in the fifth item, the liquid phase ozone, the effectiveness of the ozone water cleaning semi-monitoring gas phase odor, and the concentration of a gas emulsion. 1270920 _ Case No. 93117037_年月日日 Revision _ 6. Patent application scope 9. The system for high-performance ozone water cleaning semiconductor wafer according to claim 8 of the patent application, wherein the gas phase odor analysis unit uses gas The phase odor analyzer is configured for sampling and detection. 10. The system of high performance ozone water cleaning semiconductor wafer according to claim 1, wherein the cleaning tank discharges the used ozone water from a discharge port. 11. The system of high performance ozone water cleaning semiconductor wafer according to claim 1, wherein the cleaning tank is used for cleaning the used ozone water, and a discharge port is connected to the ultrapure water inlet through the pipeline. Recycling with Fang Lu. 1 2 . The system for high-performance ozone water cleaning semiconductor wafer according to claim 1, wherein the cleaning tank can be further improved by irradiating with short-wavelength ultraviolet light (UV) during wafer cleaning. The rate of oxidative decomposition of organic matter in the cleaning process. A system for high-performance ozone water-cleaning semiconductor wafers as described in claim 1, wherein the additive supplied by the additive supply means hydrogen peroxide (Η 20 2, hydrogen peroxide). 1 4. The system for high-performance ozone water cleaning semiconductor wafer according to claim 1, wherein the monitoring mechanism comprises: a liquid phase ozone concentration detecting unit for sampling and concentration analysis in the cleaning tank Liquid odor concentration of ozone water; an additive concentration detecting unit for sampling and analyzing the additive concentration of the solution in the cleaning tank; a pH-based detection unit for measuring the pH value of the solution and information Page 26 1270920 Case No. 93116037 Month 修正 Amendment 6. Collection of patent application scope number; A water temperature detection and control unit measures the temperature of the solution at any time and performs constant temperature control. 1 5 . The system of high-performance ozone water cleaning semiconductor wafer according to claim 14 of the patent application, wherein the liquid phase ozone concentration detecting unit of the monitoring mechanism adopts a liquid phase odor analyzer configuration sampling and analysis . The system of high-performance ozone water cleaning semiconductor wafer according to claim 1, wherein the automatic feeding control mechanism may react to the feedback data detected by the monitoring mechanism to output a control signal. The feedback control adjustment of the concentration of the gas phase ozone, the rotational speed of the power component and the gas and liquid feed ratio, and the additive additive amount, pH value and water temperature are used to maintain the cleaning solution in the cleaning tank. Stable liquid phase ozone concentration, additive concentration, pH and water temperature are the best wafer cleaning conditions. 1 7. The system for high-performance ozone water cleaning of semiconductor wafers according to claim 1, wherein the parameter control adjustment operation of the automatic feed control mechanism is performed by means of quick response and reduced control deviation Adjustment of the operating parameters of the item. 1 8. The high-performance ozone water cleaning half wafer system according to claim 1 of the patent application, wherein the parameter control adjustment operation of the automatic feed control mechanism is adopted by a parameter control software program design. 1 9. A system for high-performance ozone water cleaning of semiconductor wafers. The system architecture includes: a high-speed centrifugal gravity field device for ultrapure water and gas phase ozone Page 27 1270920 —----Case No. 93117037 _Year J----~^Correct ___, Shen Qing Patent Range Gravity Field High-quality Transfer Contact Solubility Environment to Obtain Ozone Liquid Phase Dissolved Wafer Cleaning Solution a storage tank connecting the liquid phase odor generating mechanism to obtain a cleaning solution storage; an additive supply mechanism connecting the cleaning tank to control the addition of the additive; and a monitoring mechanism disposed in the cleaning tank Instantly detect various cleaning solution application parameters during the cleaning process, and return the feedback data to an automatic feed control mechanism; _ an automatic feed control mechanism, containing the solution application parameter setting value, accepting various parameter data of the detection mechanism to detect feedback Collecting and analyzing, comparing the set standard values, and making a rapid reaction mechanism for the comparison results, and then quickly adjusting the operating parameters to maintain the optimal oxidative decomposition capacity of the solution, maintaining the most effective organic matter on the wafer surface. (such as photoresist) or other oxide layer removal, can also be used to clean the wafer in large quantities and continuously. 2 0. The system for purifying a semiconductor wafer of ozone-efficiency ozone water as described in claim 9 of the patent application, wherein the high-speed centrifugal gravity field device is a centrifugal device capable of generating a high-speed rotating crucible in the structure The gravity field is ring-shaped, forming a condition that can cut ultrapure water into small waves or mist, and then carry out the reverse phase of the gas phase ozone, complete the solution, mix and mix, and quickly dissolve the gas phase ozone. A mass transfer mechanism is obtained to obtain a high concentration liquid phase ozone aqueous solution. ' 21 · High-performance ozone water cleaning as described in claim 19 1270920 _ Case No. 93117037_年月日日__ 6. A system for applying for a patented semiconductor wafer, wherein the gravity field formed by the high-speed centrifugal gravity field device is adjusted by a change in the rotational speed. It is used to control the forced solubility between ozone and water solvent to maintain the concentration of the cleaning aqueous solution or to use different cleaning targets. 2 2. The system for high-performance ozone water cleaning semiconductor wafer according to claim 19, wherein the speed of the high-speed centrifugal gravity field device is detected by a monitoring mechanism, and The adjustment of the speed of the automatic feed control mechanism. 2 3. A system for high-performance ozone water cleaning_conductor wafer according to claim 19, wherein the liquid phase ozone concentration of the wafer cleaning solution is supplied through ultrapure water and gas phase ozone. And the speed of the high-speed centrifugal gravity field device is controlled to maintain the concentration of the cleaning aqueous solution or to apply different cleaning targets. A system for high-performance ozone water-cleaning semiconductor wafers according to claim 19, wherein the reservoir is simultaneously immersed in the cleaning work space. 2 5. A method for cleaning semiconductor wafers with high-efficiency ozone water, the method comprising: providing a high-concentration liquid phase ozone cleaning solution; • providing a storage tank in which the liquid phase ozone cleaning solution and the additive are stored and mixed; The circle is immersed in the foregoing storage tank; the liquid phase ozone cleaning solution and the additive mixture liquid are used to oxidize and clean the surface of the wafer; Page 29 1270920 曰修 - Case No. 93117037, Patent Application Scope In the aforementioned wafer cleaning process, the solvent and condition parameters of the mixed solution are immediately monitored and fed to an automatic feed control mechanism; The automatic feeding control mechanism collects and analyzes the above-mentioned feeding parameter data and reacts promptly to the rapid response mechanism, thereby rapidly adjusting the f-number of each operation to maintain the optimal oxidative decomposition ability of the solution and maintain the most effective surface of the wafer. The removal of organic materials (such as photoresist) or other oxide layers can also be used to clean wafers in large quantities and in 4, 1 (7) w, MS. 2 6 · If the application is specific; 丨丨 from the semiconductor wafer method, the high-performance ozone water cleaning according to the 25th item, the liquid phase ozone generation, the high-concentration liquid ozone cleaning solution is 27. 4 generated by the structure. The method of semiconductor wafer, which is capable of meeting the high-efficiency ozone water washing speed centrifugal gravity field described in Item 25, wherein the liquid phase ozone generating mechanism is a high-force forced mass transfer mechanism, and the X-set adopts / High-reporting in the gravitational field formed by the rotation, high-quality transmission, ultra-pure water and gas-phase ozone in the gravity field environment solution of the wafer cleaning solution gas, liquid contact dissolution 'to obtain high ozone liquid solution 2 8 · The high-performance ozone water-cleaning gravity-rotating packed bed as described in item 25 of the method for semiconductor wafers, wherein the liquid phase ozone generating mechanism is a high-pressure environment gas, liquid, and i A hollow enclosed space is provided for the gravity solution. ά , 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 以获得 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆 晶圆Additives Page 30 1270920 __Case No. 93117037_Yearly Revision _6. Patent Application Scope 3. The method of high-performance ozone water cleaning of semiconductor wafers as described in claim 25, wherein the wafer cleaning The parameter detection side of the process is performed by a monitoring mechanism disposed in the aforementioned storage tank, and the detection data is fed back to the automatic feed control mechanism. 3 1. A method for cleaning a semiconductor wafer with high-efficiency ozone water as described in claim 30, wherein the parameter detection side of the monitoring mechanism includes liquid phase ozone concentration detection, additive concentration detection, solution acid and alkali Value detection and solution temperature detection. 3 2. A method for cleaning a 10-conductor wafer with high-efficiency ozone water as described in claim 30, wherein the monitoring mechanism is configured to provide a liquid phase ozone concentration detecting unit and an additive concentration through a tank. The detection unit, a pH-based detection unit and a water temperature detection unit respectively perform sampling analysis. 3 . The method of high-performance ozone water cleaning semiconductor wafer according to claim 25, wherein the automatic feed control mechanism uses a parameter control program to quickly respond to the detection parameter value of the feedback, and The reaction control signal is made to perform parameter adjustment control. 34. The method of high performance ozone water cleaning semiconductor wafer according to claim 25, wherein the parameter adjustment control of the automatic feed control mechanism comprises: gas phase ozone generating concentration, forming a gravity field rotation speed and gas, The feedback control of the liquid feed ratio, the additive additive amount and the addition speed, the pH value and the water temperature are adjusted so that the cleaning solution can maintain a stable liquid phase ozone concentration, additive concentration, pH value and water temperature. Optimal wafer Page 31 1270920 Case No. 93116037 Month 修正 Amendment VI. Patent application scope Cleaning conditions. 3 5. A method for cleaning semiconductor wafers with high-efficiency ozone water, in a cleaning bath, using a mixture of liquid ozone solution and hydrogen peroxide as a wafer cleaning solution to oxidize and decompose the wafer surface, And the monitoring mechanism instantly detects the parameters of each solvent and condition in the cleaning solution, and feeds the automatic feeding control mechanism to perform instantaneous parameter adjustment control to maintain the optimal oxidative decomposition ability of the solution, and maintain the most effective surface of the wafer. Removal of organic materials (such as photoresist) or other oxide layers can also be used to clean wafers in large quantities and continuously. • 3 6 . The method of high-performance ozone water cleaning of a semiconductor wafer according to claim 35, wherein the liquid phase ozone solution is a gas odorizer and ultrapure water, and is subjected to a high gravity field. The mass transfer contacts the dissolved ozone water. 3 7. A method for cleaning a semiconductor wafer with high-efficiency ozone water according to claim 35, wherein the ozone water is subjected to a high-gravity field, high-quality contact and dissolution environment, and is a liquid phase ozone generating mechanism. provide. The method of high performance ozone water cleaning of a semiconductor wafer according to claim 37, wherein the liquid phase ozone generating mechanism employs a high gravity rotating packed bed. • 3 9 . The method of high performance ozone water cleaning semiconductor wafer according to claim 37, wherein the gravity field environment provided by the liquid phase ozone generating mechanism is an adjustable environment for performing different ozone The concentration of ozone water is suitable for use in different cleaning targets. 4 0. High-performance ozone water cleaning as described in Article 35 of the patent application Page 32 1270920 _ Case No. 93171037_年月日日_Amendment _ Sixth, the method of applying for a patent range semiconductor wafer, wherein the ozone water is subjected to a high gravity field, high mass transfer contact dissolution environment, and is a high speed centrifugal gravity field Provided by the device. 4 1. A method for cleaning a semiconductor wafer with high performance ozone water as described in claim 40, wherein the gravity field environment provided by the high speed centrifugal gravity field device is an adjustable environment for performing different ozone The concentration of ozone water is suitable for use in different cleaning targets. 4 2. A method for cleaning a semiconductor wafer with high-efficiency ozone water as described in claim 35, wherein the immediate detection side of the monitoring mechanism includes concentration detection of liquid ozone and additives, and pH value of the solution and Solution temperature parameter detection of environmental conditions. 4 3. The method for cleaning a semiconductor wafer by high-performance ozone water according to claim 35, wherein the monitoring mechanism comprises a liquid phase odor analyzer, a hydrogen peroxide concentration detecting unit, and a The pH value detection unit and a water temperature detection unit are composed. 44. The method of high performance ozone water cleaning semiconductor wafer according to claim 35, wherein the parameter adjustment control of the automatic feed control mechanism System, including liquid phase ozone concentration, additive additive amount, pH value and water temperature and other parameter conditions feedback control adjustment, so that the cleaning solution can maintain a stable liquid phase ozone concentration, additive concentration, pH value and water temperature, etc. The best round cleaning conditions. 45. The method for cleaning a semiconductor wafer by high-performance ozone water according to claim 44, wherein the adjustment of the liquid phase ozone concentration parameter is performed by an automatic feed control mechanism to generate concentration and form gravity for gas phase ozone. The control of the speed of the field and the gas and liquid feed ratio. Page 33 1270920 _ Case No. 93117037_Year of the month _ Amendment six, the designated representative map (1), the representative figure of the case is: Figure 1 (2), the representative symbol of the representative figure of the case is a simple description: 1 liquid phase ozone generation Institution; 2 cleaning tank; 3 additive supply mechanism; 4 monitoring mechanism; 5 automatic feed control mechanism; 6 1 pure water supply; 6 2 ozone generator Page 3