TW382004B - An on-site device, in a semiconductor device fabrication facility, for providing ultra-high-purity buffered ammonium fluoride or hydrofluoric acid to a semiconductor manufacturing operation - Google Patents

Abstract

A process for preparing ultra-high-purity buffered hydrofluoric acid on-site at a semiconductor manufacturing facility (front end). Anhydrous ammonia is purified by scrubbing in a high-pH liquor, and then combined with high-purity aqueous HF which has been purified by a similar process. The generation is monitored by a density measurement to produce an acid whose pH and buffering are accurately controlled.

Description

Printed by A7 B7, Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs,-V. Description of Invention (1) Comparison of related patent applications: US Provisional Patent Application 08 / 499,562, July 7, 1995 Background and Summary of Invention The invention relates to a system and method for supplying ultra-high purity buffered hydrofluoric acid and / or ammonium fluoride (NH4F) to semiconductor manufacturing operations. Background: Pollution in the manufacture of integrated circuits Generally speaking, pollution is a matter of great concern in the manufacture of integrated circuits. In the modern integrated circuit manufacturing process, most of the work steps are various purification steps; these purification steps may require the removal of organic pollutants, gold pollutants, photoresists (or their inorganic residues), Etching by-products, natural gas compounds, etc. Since 1999, a new front-end processor (integrated circuit wafer manufacturing equipment) usually costs more than 1 billion (1,000,000,000) US dollars, and most of these costs are used for chip control and purification. And pollution control instruments. One of the most important sources of pollution: impurities in processing chemicals. Because purification is extremely frequent and important, the pollution caused by purification chemical reactions is very disgusting. Extremely high purity levels required for semiconductor manufacturing. Rare or exclusive in industrial processes. At such a high level of purity, the handling of chemicals is tedious (of course, it cannot be completely avoided). The exposure of ultra-pure chemicals to air, particularly in environments where workers are present, must be minimized. This exposure has the risk of introducing cuts and forming pollution. Because the manufacturer's or user's premises originally had a higher risk of forming pollution, placing ultra-pure chemicals into this paper standard applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) ------ --- 〇 ---- ^-I Order ------ (Please read the notes on the back and fill out this page) A7 —__ ^ _ B7 _, V. Description of the invention (2) Lotus in a closed container Losing is still not ideal. Furthermore, undetected contamination may damage a large number of expensive wafers. Because many corrosive and / or toxic chemicals are often used in semiconductor processing, the supply place of chemicals is usually away from the workplace of the front-end processor worker. together. The piping for supplying ultra-high purity gases and liquids is well-known in the semiconductor industry for assembly and maintenance, so most gases or liquids can be transported from anywhere in the same building (or even on the same site). Manufacturing station. Ammonia purification Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The inventor of this case has developed a method for preparing ultra-high purity ammonia in a semiconductor wafer production site system , Which includes: sucking ammonia vapor from a liquid ammonia storage tank, passing ammonia gas through a micro-pumping device, and using purified water with high pH (preferably deionized water that has performed equilibrium with the ammonia fluid) The filtered steam was washed. This discovery can transform commercial-grade ammonia into high-purity ammonia, which is sufficient for high-precision manufacturing without the need for traditional tower distillation. The absorption of ammonia vapor from the supply storage tank itself is 羼 monofluorene distillation. It has the ability to eliminate non-volatile and high-boiling impurities (such as alkali metal and alkaline earth metal oxides, carbonates and hydrides, and transition metal halides). And argon, and high-boiling hydrocarbons and halocarbons). Active volatile impurities that may be found in commercial-grade ammonia, such as: some transition metal rhenium halides, Group BI metal hydrides and halides, some Group IV element hydrides and halides, and halogens, previously thought to require distillation Only those who can be removed can be removed by washing to a degree suitable for precision work. This is a very surprising discovery, because the washing tower technology is traditionally used to remove large -4-this paper size applies Chinese National Standard (CNS) A4 specifications (210 × 297 mm) 87 7. ^ μ —, 5. Description of the invention (3) Scale impurities rather than microscale impurities. Wet processing and dry processing There are many technical easiest aspects in semiconductor processing. One of them is the conversion (and attempt to change) of wet processing and dry processing. In dry processing, only gaseous or plasma-phase reactants come into contact with the wafer. In wet processing, many liquid agents are applied in different situations, such as: etching silicon dioxide or removing natural oxide layers, removing organic substances or trace organic pollutants, removing various metals or trace organic pollutants, etching nitride Silicon, etching silicon. Electro-paddle etching has many notable abilities, but is not suitable for purification. There are also no readily available chemical methods to remove some of the most undesirable impurities, such as gold. Therefore, the wet purification method is extremely important for modern semiconductor processing, and it will be so in the foreseeable future. The photoresist is present when the etching is performed and does not require subsequent high temperature processing. Instead, the resist needs to be stripped and then cleaned. · Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The substances that must be removed for purification may include: photoresist residues (organic polymers); sodium; Alkaline earth metals (for example: calcium or magnesium); and heavy metals (for example: gold). Most of these materials cannot form volatile halides, so plasma etching cannot remove them. Purification by wet chemical reaction is required.

In this way, the purity of the processing chemicals during plasma etching will not be important. Before the high temperature steps are performed, the Gein requires several purification steps after these steps. Before the high temperature steps introduce these pollutants, the purification steps can Remove hazardous pollutants. However, the impact rate of the semiconductor surface is usually a million times higher than that of plasma etching, and it is followed by K -5 immediately after the liquid purification step.-This paper size applies to China National Standard (CNS) A4 (210X297 mm) ~ Economy Printed by A7 B7, Consumer Cooperatives of the Ministry of Standards, Ministry of Standards of the People's Republic of China. 5. Description of the invention (4) The high temperature step, the purity of liquid chemicals is very important. In any case, wet processing has a major disadvantage, namely ionic contamination. The structure of the integrated circuit uses only a few kinds of dopants (boron, hafnium, phosphorus, and meta or antimony) to form the required P-type and η-type doped regions. But many other kinds of adulterants are those that are electrically active and hurt extremely undesirable pollutants. At concentrations far below 10 13 / cm 3, many of these pollutants may have toxic effects, such as increased contact leakage. Furthermore, some of the less popular pollutants condense into the silicon, that is, when the silicon comes into contact with an aqueous solution, the equilibrium concentration of the pollutants in the silicon will be higher than that in the solution. In addition, some of the less popular pollutants have extremely high diffusion pseudo-numbers, so introducing these dopants into any part of the silicon wafer may allow these pollutants to diffuse around, including contact sites, where Contaminants will cause electrical leakage. Therefore, it is best to keep all metal ion contents of all liquid solutions used on semiconductor wafers at a minimum level. The total concentration of all metals is less than 300 値 trillion points, and any kind of gold 靥 is better than 10 値 trillion points, especially the lower the concentration, the better. In addition, pollution caused by cations of yin and yang must also be controlled. (Several anions may have a harmful effect, for example: a mismatched metal ion may be reduced to a mobile metal atom or ion in a silicon lattice). Front-end facilities often include on-site purification systems for the preparation of high-purity water (deionized water). But it is even more difficult to obtain processing chemicals with the required purity. Buffered hydrofluoric acid and / or ammonium gasification for semiconductor manufacturing. Innovative rules and methods generated on-site. The paper's dimensions apply to Chinese National Standard (CNS) A4 (210X 297 mm). (Please read the notes on the back first Fill in this page again.) 1T ------ #-· V. Description of the invention (A7 B7 Printed by the Department of Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy The average I can be, in the row. Pollution by a good combination system was lowered to the Duan Tashi system. In the system, the pseudo-top was obtained with the most joint hydrogen grid and must be leveled. Nearly pure bars β were set. The chemical process of chemical reduction and catalysis is pure and high-quality, and the method of washing and purifying hydrogen and hydrogen and fluorine is required. The method of washing is shown below. The method of acidification is based on the need to dye and the body. The square section is mixed with acid, sulphur, fluorine, and fluorine. It is a decontamination of the industry. The two or two J fluorides added to the economic construction office have been severely upgraded. The body should be arsenic, and the same should be used for ammonia. Mildly 2) It can be used as a guide for alkaloids. In pure decontamination, F pure aF guide dyeing super-like its semi-presently approved mixed-use point saves the super, internally high (C and pollution is the city, the quality is better than others, and the cocoa can be used to prepare the middle tower. In addition, the miscellaneous materials are in different systems, such as the system. For example, cleaning, fluorine production, low-hydrogen systems, etc., the use of the included strips are due to acid washing, which can polarize the arsenic surface. The number of packages is equal to the equivalent. It seems that the operation tower of the gas department has a square amount of fluorine type. Many products in the meter body will send the machine's hydrogen gas to the hydrogen purifier containing arsenic. Reason: The first stage of washing the fossils is pure and contains half of the passed-through, and the current group must be in the Department of Chemistry. The fluorocarbon system is made in the Ministry of Commerce. Dihydrate hydration application material C before the addition of pure and profit-removing pure tube was high in the solubility of the original non-fluorinated product and so on. It is hydrogen acid. The gasification tower was originally designed to be light and fully prepared. This is based on α. The gas and hydrogen are distilled to make the common system 5¾ due to local conditions. The public place is divided into separate products. Non-internal to dry 10. Fortunately, raw materials and No. 1 (Please read the notes on the back before filling in this page.) This paper is again applicable to the Chinese National Standard (CNS) A4 (210X297 mm). The consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs has been printed by A7 B7. 5. Description of the invention (6) Elimination of pollutants not removed by the fractionation column, and finally hydrogen fluoride or ammonium fluoride

V supply. ....-By adding an oxidant [KMn〇4 or (NH4) 2S2〇8] and a cation (for example: KHF2) to form ®K2AsF7, God will become a positive pentavalent state and remain during the distillation In the evaporator. This will be a batch-wise method, so the reaction is slow, and it takes sufficient time to complete the reaction before performing the distillation. At nominal temperatures, the contact time required for this procedure is approximately 1 hour. In a continuous process, the completion of the reaction will require high temperatures and pressures (not desirable for safety reasons) or large vessels and piping. In this procedure, hydrogen fluoride is sent to a batch evaporator and treated with a gasifying agent, with constant stirring and a desired reaction time.

After C, hydrogen fluoride is distilled in a fractionating column having a reflux, thereby removing the entire metal impurities. Those who achieved significant reductions during this step include: Group 1 (I) Sodium Group 2 (I) Calcium, Samarium, and Barium Groups 3 to 12 (HA to IA) Chromium, tungsten, molybdenum, manganese, iron, copper Zinc Group 13 (M) Gallium Group 14 (IV) Tin, Lead, and Group 15 (V0) Antimony. The function of this fractionation column is equivalent to many simple distillations in a row. To achieve this effect, the column is filled with a material with a high surface area and the liquid is reversely flowed to ensure that a complete balance is achieved between the descending liquid and the rising vapor. Only a part of the condenser was installed in the column to provide reflux, and then the purified gaseous hydrogen peroxide was introduced into the hydrogen fluoride ion type purifier. Except for possible inclusion of arsenic, this paper size applies Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (please read the precautions on the back before filling this page) ^ ------ Order

C Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___B7 V. Description of the invention (7) Chemicals may need to be quenched to remove these chemicals i In accordance with normal standards t This phase of hydrogen gas has been It is considered to be pure. In the introduction and supply system of hydrogenated gas, V 1- 刖 »will use hydrogen fluoride ion type purifier to ensure higher purity. Certain elements may be present in the treatment solution or introduced into the ion type purifier. Sulfate inclusions in the gaseous gas absorbing fluid ΠΏΐ. Tests in the ionic purifier show: The pollution levels of the following elements in the hydrogen fluoride gas flowing body have been greatly reduced: Group 2 (I) Strontium and Barium * Groups 6 to 12 (VI A to IA) Chromium tungsten and copper 9 Group 13 (1 I) Boron 9 Group 14 (IV) Lead-tin * and Group 15 (V) Antimony 0 Many of these elements are very useful in guiding the elimination of God's pollution. 0 Entrainment in the distillation column due to excessive content in the stele processing operation »It can be removed by rectification in this step. 0 Please note / ¾¼ is * If hydrogen fluoride with a low arsenic content can produce 9 batches, the step of removing the stele can be eliminated. 0 White 1995 This raw material produced by United Chemical Company can be purchased on the US market. On-site preparation of buffered hydrogen acid and ammonium fluoride as described above i Hydrogen acid (HF) is a very important processing chemical for the pseudo-semiconductor manufacturing industry. 0 The hydrogen acid is often in the form of a buffer 9 in use to reduce the increase in etching by-products. PH change caused by acid load 0 (Hydrogen acid reacts with silicon to produce fluorosilicic acid. The strong acid will change the pH of the solution » Dynamic etching rate 0) is applied to certain acids for these reasons (please read the precautions on the back before filling this page) The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) B7 V. Invention Explanation (8) The source of the buffer effect of the printing of the consumer cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs is the source of the delay. According to the ammonia gas that is blown into the square ammonia, hydrofluoric acid and hydrofluoric acid are different. The Mohr diagram of the period is briefly described in this case. The diagram is for reference. The diagram is simple. Figure 1 shows this picture. _ 2 different * Figure 3A It is fluorine Figure 3B1 is Figure 3B2 is Figure 3B3 is Figure 4 is a well-known person; but to produce more problems, κ must be pure enough to extract some of the acid solution in hydrofluoric acid. It is made by reforming a specific acid solution. The method includes Yuan Chong hydrofluoric acid and acid mole ratio. Ammonium fluoride has more HF moles. The ratio of the two on the concentration instrument. For ultra-high-purity chemicals, buffers and gein buffers are also pollutants that reduce the effectiveness of the system. The shock effect is usually provided by an ammonium component in the IU embodiment. Buffered hydrofluoric acid can be obtained by using ammonium fluoride. The only difference is that the molar ratio of the solution is 1.00, and the equipment used in the slow solution is the same. The setting K achieves the inventions disclosed in advance. It will be described with reference to the attached drawings, which shows specific embodiments of the invention and is also incorporated in this specification. 0 'Description: The process of inventing the ammonia purification unit, the semiconductor production process, Flow chart of the ammonia generator, FIG. 3A, a specific embodiment of the process, FIG. 3A, another specific embodiment of the process, FIG. 3A, another specific embodiment, a representative specific example: hydrogen fluoride distillation / ion type purifier generator. -10-This paper size applies to Chinese national standard (CNS> Α4 specification (210 × 297 mm) Please read back-Note

I Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (9) Detailed Description of the Specific Specific Embodiments: For many innovations of this patent application, special reference will be made to the current ideal specific embodiments (only examples) Description, but by no means limited to this), in which: Purification of ammonia According to the present invention, ammonia is first taken out of the vapor space of a liquid ammonia supply storage tank. Withdrawing the vapor in this way, several solids and high-boiling impurities are left in the liquid phase, as in the same single-stage distillation. The supply tank may be any conventional supply tank or other storage tank suitable for containing ammonia, and the ammonia may be anhydrous or an aqueous solution. The tank can be maintained at atmospheric pressure or, if necessary, at a pressure higher than atmospheric pressure so that ammonia can easily flow through the system. It is best to control the temperature of the storage tank so that the temperature range is between about 10 t: and 5 Ο υ, but preferably between about 15 t: and 35 ，, especially between 20 t: and 25 C. good. Impurities removed as a result of ammonia being taken out of the vapor phase include Group I and Group I gold moths in the periodic table and the amidates formed by these gold hurricanes upon contact with ammonia. In addition, the oxides and sulfonates of these metals; and hydrides such as: hydrogenation and hydrogenation IM; group I elements and their oxides, and hydrides and halide ammonium adducts of these elements ; Hydrides of transition metal; and heavy hydrocarbons and halogen compounds, such as: pump oil. The ammonia taken from the storage tank is passed through a filter unit to remove any solid matter entrained by the vapor. The membranes of the microfiltration and ultrafiltration units are commercially available and can also be used. The choice of filter material grade and type is determined according to needs. The current preferred embodiment is the use of a coarse filter in the ionic purifier-11-this paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before filling this page ) Order Φ. A7 B7 Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Printed by Consumers ’Cooperatives. 5. Description of the invention (1 0) 1 I after passing through the 0.1 Sami filter f, and Jar without I after I 1 Filtration effect Ⅰ Pass the filtered steam through a washing tower »Use high acid in the washing tower, please wash the steam with 1 alkalinity purified (preferably deionized) water 0 The water with 1 alkalinity is best to be an aqueous solution of the atmosphere.> By using it in the washing tower to carry out the recurring attention 1 | ring effect to increase the concentration to saturation. 0 The washing tower can be washed in the traditional way. Convection mode for easy operation 0 Although the operating temperature is not Important 9 But the washing item is refilled and 1 'The operating temperature range of the polyester tower is preferably about 10 v to about 50 〇9, especially about 15 It is written,! /'-* · — To about 3510 is better Ground 9 The operating pressure is also not important 9 but the desired operation page 1 1 The operating pressure range is from atmospheric pressure to about 30 psi above atmospheric pressure I 0 Usually the tower contains traditional scrubbing tower packing to provide liquid and gas space The height contact of 1 1 preferably also includes a defogging section. 0 1 is set at one hundred > · Α. In the combined embodiment, the filling height of the tower is about 3 feet 1 1 (0.9 meters) and within. The diameter is about 7 inches (18 cm) to achieve a filling volume of 110.84 cubic feet (24 liters). 9 The pressure drop during operation is about 0.3 o'clock (1 1 0. 07 5 Pascals), Its overflow is less than 10¾. And in the case of an overflow of 20¾ 1 1 »its nominal recirculation flow is about 2.5 plus life / min. < (0. 16 liters / second) / also V or 5 plus m / minute (0 · 32 2 liters / second), in which the gas wound enters 1 I below the ballast > and the liquid flows from the filler The upper part and the lower part of the grate section enter 0. The aSft filling material used in the washing tower described in this I 1 case has a nominal size of less than one eighth. 1 One tower diameter. 0 The defogging section of the tower has a similar or denser structure. Filler 1 1 1 and pseudo another traditional structure. 0 should be understood »All descriptions in this paragraph F 1 and dimensions are only pseudo examples. 0 Each parameter of the system can be changed. 0 1 I In typical operation ) At the beginning, the deionized water is saturated with ammonia 1 1-12-1 1 1 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (11) Concave like hydrogen halide Formulas issued ο open examples with available base. For example, the twirling strips of the 20-liter package are also often towering, and the property is Lianhuazai. It can be turned into semi-pure gold. About the assimilation Zhonglianzhong, the halogen or ammonia, the imperfect conversion of the period of accumulation of the VI type. Fanliu-type strips of lotus roots, distant antimony, enthusiasm, and other steps, the distillation process is deactivated and combined, and the system is special. The steaming batch tower is removed: arsenic, and the strip is special. The separation is based on the broader formula containing ®, which should be used for profit. The first batch of phosphorus-containing coatings is widened and then settled. . As an example, and Fen Lian has a regular ground gas quality formula 3)., According to the formula can ammonia. Intentional steaming is more continuous. Intermediate SH substances can be used, and the time system will continue to clean up the period of time (A chemical can be connected and the combination is less than the chemical element half-wash week heterohydrogen half semi-main field?!-/ Use The former or the first production of the single or multiple MW applications with distillation from the beginning to remove arsenic and gold, not much ammonia, should be entangled into the body to remove and cross. Burma and big. M's continuous crop (Liquid tower 4) The conversion of the passing object and the connection rate, the prediction and the liquid quantity are as follows. The reason is that when Θ pure ammonia is used, the formula S is less soluble. One hydrogen, but it should be treated as a single batch. ί by alkane, and to. Sekiji / < 1 due to tower, water is divided into inner sands and turned into pre-washing-shaped grooves for removal of western polyester .: Huahua Lianzhi Mingxi washes a word (please read the precautions on the back before filling this page) ) The operating pressure printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs may be 300 psi (2,068 仟 pascals), with batch sizes of 100 lbs (45.4 kg). The diameter of the washing tower in this example is 8 inches (20 cm), the height is 72 inches (183 cm), the operating overflow is 30¾, the steam velocity is 0.00221 feet per second (0.00067 meters per second), and the height is equivalent to one 1.5 inch (3.8 cm) theoretical board and 48 値 equivalent board. The dimensions of the boiler in this example are: approximately 18 inches (45.7 cm) in diameter, 27 hours (68.6 cm) in length, a reflux ratio of 0.5, the temperature of the recirculated cold water entering is 60 degrees (1 5.61), and the temperature when leaving For the 90T (32.2t:) e again emphasized -13 _ This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1 2 ) 1 1 One point is that this is only an example — the structure of the distillation column is very extensive and 1 | the operating parameters can be used 0 I depending on its use t purified ammonia »whether or not distillation first 1 step 9 available Action-Purified gas or used as an aqueous solution C In this case reading 1 back 1 t The purified ammonia is pseudo-dissolved in 1 of purified (preferably deionized) Note | Water) 〇 I matter I Figure 1 The display is the flow chart of the early purification of the ammonia of the present invention. 0 Liquid ammonia items are refilled. 1 傺 傺 stored in the storage tank 11 〇 ammonia vapor 12 僳 take the vapor space 9 of the white storage tank) and then pass a shut-off valve 13 * Then pass through a filter 14 0 filtered ammonia vapor page 1 I 1 5 (the flow rate is controlled by-* pressure regulator 16) t is introduced into a washing column 17 1 | 9 This washing column contains a packed section 18 and A defogging pad 19 0 When the ammonia vapor flows upward 1 丨 The saturated ammonia solution 20 flows downward 9 The liquid is circulated by the circulating pump 1 Order 1 2 1 The liquid level is controlled by a liquid level sensor 2 2 0 Waste 23 is periodically excluded from the liquid accumulated in the bottom of the washing tower 0 Deionized water 1 1 24 僳 is supplied to the washing tower 17 The high pressure is maintained by the pump 25 0 Washed 1 | Ammonia 26 pseudo-oriented three One of the flow paths. The flow paths are 1 1 (1) — * distillation column 27 9 The internal ammonia can be further purified. 0 The distilled ammonia 28 is redirected to the place of use. 0 1 I (2) Dissolved C3B early 29 9 where ammonia is combined with deionized water 30 to form a water 1 1 solution 31 9 and then redirected to Use site 0 If the plant operation has multiple uses 1 I site t The aqueous solution can be collected in a temporary storage tank f and then the temporary storage tank 1 will send ammonia to the pipeline to each use site in the same factory 0 I 1 (3) Conveying line 32 * This conveying line sends gaseous ammonia to the place of use 0 ί 1 The above second and third flow paths > Among them, no distillation column 27 9 is suitable for production 1 1-14-1 1 Applicable to Chinese national standards (CNS> A4 specification (210X297 mm)

V. Description of the invention (13) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Ammonia with metal impurities below 100 値 trillion points. However, it may be advantageous to include a distillation column 27 in certain applications (for example, several furnace purification applications). Examples are: the use of ammonia in a furnace or chemical vapor deposition (CVD). For example, 2, ammonia is used for chemical vapor deposition, and distillation column is used to remove non-condensable substances, such as gas and nitrogen, because it may interfere with the chemical vapor deposition effect. In addition, because the ammonia industry and water in the washing tower 17 are saturated, depending on the characteristics and efficiency of the distillation tower, a dehydration can be added between the washing tower 17 and the distillation tower 27 in the system. unit. Regardless of any such flow path, the resulting fluid, gaseous ammonia or water, may be further divided into two or more substreams, each of which is directed to a different one. The use station, so the purification unit can simultaneously supply Purified ammonia is used by many stations. Purification of hydrogen gas' Fig. 4 (a) shows an on-site hydrogen fluoride purifier in accordance with a representative embodiment of the innovations shown. After the purification of hydrogen gas is completed, arsenic is first oxidized to a positive pentavalent oxidation state, and then fractionated to remove the As + 5 and gold osmium impurities. Please refer to U.S. Patent 4,929,435 for reference. As shown in the literature, many different gasifiers have been used to achieve this project, please refer to the following patents and patent applications, all of which are hereby incorporated by reference: US # 3, 68 5 , 370; CA81-177347s; EP # 351,1 07; JP # 61-151, 002; CA74-101216; CA78-23343; US »5,047,226; USSR # 3 7 9,533; CA8 1-1 77348 t; US # 4,954 , 33 0; UStt4, 9 5 5, 43 0 -15-This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back first and write this page.) IT- ----- IP- · A7 B7 V. Description of the invention (14); EPff276,5 42; US # 4,083,4 41 5 ¾ CA98-P200672f〇 It has been shown that fluorine gas (F2) is effective (published by other scholars and experts Works), and is recognized as the current desirable embodiment.卩 2 requires expensive plumbing work and safety protection, but it has been shown to be effective. Another desirable specific embodiment is the use of ammonium persulfate [(nh4) s208], whose ultra-high purity is readily available on the market. Usually, the desired oxidant, 傜, does not introduce gold 羼 atoms. So other options include hydrogenated hydrogen and ozone. Another less desirable supply is pseudo-Keros acid (persulfuric acid, h2so5, which produces hydrogen peroxide in its aqueous solution). Another option is pseudo chlorine dioxide, but its serious disadvantage is its explosiveness. Other options include nitric acid and chlorine, but both can introduce anions, which must be separated. (It is not as important to reduce the content of non-gadolinium ions as it is to reduce the content of gold ions, but it is still hoped that the content of anions will reach 1 billion points or less. The initial introduction of anions will increase the load of the ionic purification stage. Central standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperative (please read the notes on the back before filling out this page). Signar of United Chemicals, in cooperation with the inventor of this case, uses a The initial arsenic gasification step has successfully produced ultrapure hydrogen fluoride. The inventors of this case were not familiar with all the steps of the procedure, but the achievements of United Chemical Company in this area further confirmed the feasibility of the inventions shown. Permanganic acid The most commonly used oxidant for potassium injury, if another ionic purifier shown is added and hydrofluoric acid is applied. Destillation, it is predicted that it can also be used for ultra-purification. However, this product makes the cation load of the purifier greatly Increased, so the oxidant without gold tincture is more desirable. -16-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B 7 '' V. Description of the invention (15) In another specific embodiment / high purity 4 9¾ hydrofluoric acid, which does not actually contain arsenic, can also be used. Since the third quarter of 1995, Low arsenic raw materials are commercially available and can be combined with on-site ionic purification methods that do not contain arsenic oxidants to implement on-site production of ultra-pure hydrofluoric acid. The hydrogen fluoride processing flowchart includes a batch arsenic removal and evaporation stage A fractionating column to remove most of the other impurities, an ionic purifier to eliminate the pollutants removed by the non-k fractionating column, and the final hydrogen gas supplier. By adding an oxidant [KMη04 or (NH4) 2 S2 08] And an oxygen ion source (such as KHF2) to form the salt K2AsF7, arsenic will become a positive pentavalent state and remain in the evaporator during the distillation process. This will be a batch method, so the cover is slow to react. Sufficient time is required to complete the reaction before distillation. At nominal temperature, the contact time required for this procedure is about 1 hour. In a continuous procedure, high temperature and high pressure are required to complete the reaction. Use) or bulky containers and piping. In this procedure, under constant stirring with the hope that the reaction time is appropriate, hydrogen fluoride is sent to a batch evaporator and treated with a gasifier. After that, a The fractionation column distills hydrogenated gas, thus removing the entire metal impurities. Those who have achieved significant reductions during this step include: Group 1 (I) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Please fill in this page again) Group 2 (I) Calcium, Strontium, I Bay Groups 3 to 12 (MA to HA) Chromium, Tungsten, Molybdenum, Manganese, Iron, Copper, Zinc Group 13 (I) Gallium, Section Group 14 (IV) tin, lead, and group 15 (VH) antimony. -17-This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 5. Description of the invention (1 6) The fractionation The function of the tower is equivalent to a series of early distillation5. To achieve this effect. I. The tower is filled with a high surface area material9 and the liquid flows in the reverse direction9 to ensure the completion of the falling liquid and the rising vapor. Fully balanced 〇 Installed in this column only-Partial condenser to provide reflux 9 After »Purified gaseous hydrogen fluoride is introduced into the hydrogenated ion-type purifier 0 Except for possible entrained chemicals or quenching operation In order to remove these chemicals 9 According to the normal standard 9 The hydrogenated gas at this stage has been regarded as pure. The gaseous hydrogen gas is introduced into the supply system. Λ-Λ. 刖 > The gasified hydrogen ion type purifier will be used In order to ensure a higher purity, 0 certain elements may be present in the treatment solution or introduced into the ionic purifier to absorb the sulphate inclusions in the body of the gasified hydrogen flowing. 〇 Tests in the ionic purifier have shown: The following elements The level of pollution in the gaseous hydrogen gas flowing atm has been greatly reduced: Group 2 (I) 缌 and Barium Groups 6 to 12 (VI A to IA) Chromium m and Copper 9 Group 13 (I) Boron 9 Group 14 (IV) Lead > Tin »and Group 15 (V) Antimony 0 Many of these elements are very useful in guiding the elimination of arsenic pollution The entrainment in the distillation column can be printed at the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). This step removes it by distillation. The gasification of argon in the final product is as described below. Many elements form low boiling fractions with hydrogen fluoride above the aqueous solution: Group 1 (I) Sodium and potassium, ** 18- This paper standard applies to Chinese National Standards (CNS) A4 specifications (210X297 mm) V. Description of the invention (1 7) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, printed in the first half of the year, distillate the supply of ammonia, gas, and so on. Degree can be pure and tube steaming method tower :. One removes the chemical dissolving guide device, it is equipped with Duan Dian, for the system of defluorinated hydroelectricity. In this picture, I) stage washing, ballast extract strips. Its tower. Production field-< The iron is the first example, the hydrogen of the carburetor. 现 The formula of the current material process: use one to enter the production process} pure chemical transformation, the original flow} mold ¾ to be practical The examples of the starting acid in the PFM type fluorine repair are: hydrogenated U-subsidiary hydrogen is aerated from the same example (all towers and chemical products can be purely ionized, and the hydrogen content in the reservoir is not good.) The field of fluorine U is washed at a slow speed with real scattered elements. 9- Calcium, iron and aluminum are measured Π5Φ, the image body. The addition body is a single retarder, hydrogen, 19, and it can be used for production after the action of super acid. Jinhuadi-will be the first fluoride U-channel acid to produce 3AA dry gas, dehydrogenated, divided into ring. Another fluorine. In the picture, if there is more, the hydrogen produced by the distillation Department of Department: The rate of cleavage of this method is 111. The acidity of the new step is controlled by the new step. The acidity is instant. The segmentation is large and the concentration is absent) 0 indicates that the gas is reversible and the hydrogen is significantly degraded (I (VD (I Remove Feigan Yaoyin fluorine-free 3A lead to B2. The heavy-duty 2813 is best installed in the steam removal tower if it must be replaced in the pure middle hydrogen chart. The M3 chart is the first one. For example, 1 device is in motion. The element of the pseudo guide tower should be divided by the slow gas 3B instrument (please read the precautions on the back before filling this page) The paper size applies to the Chinese National Standard (CNS) A4 Specification (210X297 mm) A7 B7 " V. Invention description (18) Lotus is turned under saturation of about 105¾, so these "light" impurities escape at the top of the tower. This second washing tower can produce high purity Hydrogen acid. In the presently preferred embodiment, the liquid volume of the ammonia gas purifier is 10 liters, and the maximum gas flow rate is about 10 standard liters / minute. The washing liquid is sufficiently rinsed (continuous or incremental) ), At least once every 24 hours. Product concentration (in the two production steps) is measured with sound velocity measurement equipment (Massa (Produced by the laboratory)-concentration measurement-but other measurement methods use conductivity, density, refractive index, or infrared spectrum. When setting the processing program, you must determine the concentration of hydrogen fluoride and ammonia dissolved in water. For example, 1 kg 40¾ weight A solution of ammonium fluoride will contain 400 grams of ammonium fluoride and 600 grams of ultrapure water. Because the molar ratio of hydrogen fluoride to ammonia in pure ammonium fluoride is 1: 1, 400 grams of ammonium fluoride will contain 216 grams of anhydrous hydrogen fluoride And 184 grams of anhydrous ammonia. (Ammonium fluoride molecular weight = 37, hydrogen fluoride molecular weight = 20, ammonia molecular weight = 17). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (谙 Read the precautions on the back before filling this page) Under Hydrogen When the acid preparation process is completed, 216 grams of hydrogen fluoride is dissolved in 600 grams of water, or a concentration of 26.5¾ by weight. On-board instrument control can add hydrogen fluoride to achieve the desired concentration. Another way is to use 49¾ concentration of hydrofluoric acid Dilute to this concentration. After the 26.5¾ concentration hydrogen fluoride aqueous solution is formed, add 189 grams of ammonia to make a 40¾ concentration aqueous ammoniated ammonium solution. For different applications, other concentrations and Morse ratios can be set by concentration instrument control. Modifications and Changes -20-This paper size applies to China National Standard (CNS) A4 (210X297 mm) Employees' Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Print A7 B7 V. Description of Invention (1 9) If you are proficient in this technology #, the innovative concepts described in this patent application can be modified or changed according to the different applications, so the patent is granted The technical content of the application is by no means limited to the listed examples. For example, the innovative technologies shown are not strictly limited to the manufacture of integrated circuits, but can also be applied to the manufacture of discrete semiconductor components, such as optoelectronics Device and power supply unit. Taking another example, the innovative technology shown can also be applied to other technical aspects of manufacturing using integrated circuit manufacturing methods, such as: thin-film magnetic heads and movable dot-matrix liquid crystal displays; but their main uses are pseudo-integrals. For circuit manufacturing, other uses of the technology shown are secondary. For another example, the use of a scrubber for liquid-gas contact is not strictly required; a foamer can be used instead, but its gas / liquid contact is poor, although it is unavoidable. In addition, it is optional: other separate filtration or multi-stage filtration can be combined with the purification equipment shown. It should be noted that, although the currently desirable specific embodiments do not do so, several additives may be added to the purified water if necessary. As mentioned above, the main embodiment is a field purification system. Another way is that, in another group of less desirable embodiments, the purification system shown can also be applied to operate some manufacturing units to produce ultra-high-purity chemicals for preparation, but 'this workaround is specific The examples do not provide the advantages of on-site purification described above. As mentioned above, these applications will encounter the inherent risks of handling ultra-high purity chemicals; but for those that need to be packed _ 21, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) --- ----- ΙΓ; -------. 玎 ------ Φ, '(Please read the notes on the back before filling in this page] 87 7. 3 Λ7 B7 V. Description of the invention (21 ) Description of the printed components of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: Figure 1: 11 Storage tank 22 Liquid level sensor 12 Ammonia vapor 23 Waste 13 Close valve 24 Deionized water 14 Filter 25 Pump 15 Filtered ammonia vapor 26 Washed Ammonia 16 Pressure regulator 27 Distillation tower 17 Washing tower 28 Distilled ammonia 18 Filling section 29 Dissolving unit 19 Defog pad 30 Deionized water 20 Saturated ammonia solution 31 Aqueous solution 21 Circulating pump 32 Conveying pipeline Figure 2:-31 Ammonia water 52 Wafer holder 32 Pure gaseous ammonia 54 Acid purification station 41 Destillation station 55 Hydrochloric acid aqueous solution 42 Hydrogen peroxide aqueous solution 56 Hydrogen peroxide aqueous solution 43 Sulfuric acid 57 Rinse station 44 Rinse station 58 Drying station 45 Purifier 59 Dilute hydrogen fluoride Acid 46 Hydrogen peroxide solution 60 Rinse station 47 Mixture 61 Wafer or wafer batch-22-1-(Please read the precautions on the back before filling out this page) This paper size applies to China National Sample Standard (CNS) A4 specifications ( 210X297 mm) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 公 1 · Λ7 B7 t V. Description of the Invention (22) 48 Aqueous hydrogen peroxide solution 62 Generator 49 Mixture 63 Robot 50 Washing station 64 Chrysanthemum purifier 51 crystal Circle 65 Hydrogen Fluoride Tank Figure 3A: 14 Passager 73 Ventilation 30 Deionized Water 74 Product Outlet 71 Ammonia from Ion Purifier 75 Acoustic Sensor 72 49% Hydrogen Fluoride Supply 76 Heat Exchanger Figure 3B1: 45 Pump 86 Program Control .71 Ammonia from the young purifier 87 Pneumatic valve 81 Pure dry air '88 Control room flush 82 120 Volt AC power 89 Helium 83 Nitrogen supply 90 Supply chamber 84 Exhaust 91 System exhaust port 85 Port 92 supply chamber groove Figure 3B2: 11 storage tank 91 system discharge port 30 deionized water supply 92 supply chamber groove 59 49% hydrofluoric acid _ 22-2 ~ (Please read the notes on the back before filling out this page) The size of the paper used for the edition is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 87 7. 3 Λ7 B7 V. Description of the invention (23) Figure 3B3 : 76 heat exchanger 94 cooling water supply 92 supply chamber recess 95 cooling water return 93 ammonia fluoride outlet Figure 4: 23 waste 97 ventilation 62 generator 98 anhydrous hydrogen fluoride 74 product 99 tower 75 sensor 100 passivation tower 76 heat exchanger 101 Boiler 96 reflux condenser (please read the back and pay attention to the matter before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -22-3-This paper size applies to China National Standard (CNS) A4 specifications (2 彳0X297 mm)

Claims (1)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs · A8 B8 C8 D8 ^, patent application scope i. A gauge for providing ultra-high-purity buffered saddle fluoride or hydrofluoric acid to a semiconductor manufacturing operation in a semiconductor device manufacturing facility The device includes: a first evaporation source, which receives a hydrogen fluoride source via connection K and provides a hydrogen fluoride vapor stream there; a second evaporation source, which receives a liquid ammonia source via connection K, and provides ammonia from there A vapor flow body; the hydrogen fluoride vapor flow body is connected to pass through a first ionic purifier unit, which provides a large amount of recycled high-purity water (containing a high concentration of hydrogen fluoride) in contact with the hydrogen fluoride vapor flow body, wherein the The first purifier passes the purified hydrogen fluoride gas; and the ammonia vapour stream passes through a second ionic purifier unit through K, which provides a large amount of recycled high-purity water (containing a high concentration of ammonium hydroxide) In contact with the ammonia vapor flowing body, wherein the second purifier passes the passivated ammonia gas; a first generator unit is connected through the M The hydrogen fluoride vapor stream from the first purifier is combined with high-purity acidic deionized water to produce ultra-pure hydrofluoric acid, and the first generator unit also tops off the impure hydrogen fluoride gas contaminated by slight impurities. The fluid passes; the ultra-pure hydrofluoric acid and the ammonia vapor flowing body are connected to a second generator through the connection M, the generator causes the ammonia vapor to be incorporated into the ultra-blunt hydrofluoric acid to produce a concentration of all metals Ultra-pure buffered hydrofluoric acid with a concentration of less than 300 trillion points and a concentration of any metal below 10 trillion points; and a piping connection group that distributes the aqueous solution to each use point in a semiconductor device manufacturing facility. -23-This paper; ^ degree applicable + national national standard (CNS) 8 4 ^ (210X297 mm) (Please read the precautions on the back before filling out this page) l. Packing. Orders for consumption by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by a cooperative · A8 B8 C8 D8 ^, patent application scope i. A gauge device that provides ultra-high-purity buffered saddle fluoride or hydrofluoric acid to a semiconductor manufacturing operation in a semiconductor device manufacturing facility, including: a first An evaporation source receives a hydrogen fluoride source via connection K and provides a hydrogen fluoride vapor stream from there; a second evaporation source receives a liquid ammonia source via connection K and provides an ammonia vapor stream from there; the hydrogen fluoride vapor The fluid is connected to pass through a first ionic purifier unit, which provides a large amount of recycled high-purity water (containing a high concentration of hydrogen fluoride) in contact with the hydrogen fluoride vapor flow, wherein the first purifier enables purification Hydrogen fluoride gas passes through; and the ammonia vapour stream passes through a second ionic purifier unit through K, which provides a large amount of recycled high-purity water (containing high concentration Ammonium oxide), which is in contact with the ammonia vapor stream, wherein the second purifier passes the passivated ammonia gas; a first generator unit, which is connected to receive the hydrogen fluoride vapor stream from the first purifier and It is combined with high-purity acidic deionized water to produce ultra-pure hydrofluoric acid, and the first generator unit also passes the top fraction fluid of impure hydrogen fluoride gas contaminated with slight impurities; the ultra-pure hydrofluoric acid and the ammonia vapor The mobile body is connected to a second generator through the connection M, which causes the ammonia vapor to be incorporated into the super-blunt hydrofluoric acid, so that the concentration of all metals produced is lower than 300 trillion points and the concentration of any one metal is low Ultra-pure buffered hydrofluoric acid at 10 trillion points; and a piping connection group that distributes the aqueous solution to each use point in a semiconductor device manufacturing facility. -23-This paper; ^ degree applies + national national standard (CNS) 8 4 ^ grid (210X297 mm) (Please read the precautions on the back before filling in this page) l · Packing. Order A8 B8 C8 D8 VI. Application Scope of patent 2. For example, the Horiba device of the first patent application park, wherein the hydrogen fluoride source includes anhydrous hydrogen fluoride. 3. For the field device of the patent application No. 1 of the patent field, all of these large quantities of recycled high-purity water do not contain any additives. 4. The on-site device of item 1 in the scope of patent application, wherein the hydrogen fluoride source is substantially free of arsenic. 5. The field device as claimed in item 1 of the patent application, wherein the hydrogen fluoride source uses an ultra-pure arsenic-free hydrogen fluoride aqueous solution. (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -24-This paper size applies to China National Standard (CNS) A4 (210X297 mm)