TW557356B - Endpoint detection by chemical reaction - Google Patents

Abstract

This invention is directed to semiconductor processing and more particularly to the detection of the endpoint for removal of one film overlying another film.

Description

557356 A7 ----- V. Description of Invention (1) Ju application filed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This invention relates to the following co-pending US patent applications: Serial No. 09 / 073,605, Lawyer's Case Catalog BU9- 97-096, whose title is "Indirect Endpoint Detection by Chemical Reaction"; Serial No. 09 / 073,601, Lawyer's Case Catalog BU9-97-098, whose title is, "Endpoint Detection by Chemical Reaction and Light Scattering"; 09 / 073,607, Attorney's Case Catalog FJ9-98-050 Academic Reactions and Reagent Endpoint Detection "; Serial No. 09 / 073,603, Attorney's Case Catalog f! 9_98-061 Reduction of Product in Solution; Serial No. 09 / 073,604, Attorney's Case Catalogue FI9-98-062 Endpoint detection between academic reaction and chemiluminescence "; Serial No. 009 / 〇73,6 06 'Attorney case list FI9-98-067 Endpoint detection of academic response and photoionization"; and serial number 09 / 073,602, Lawyer's Case Catalog BU VII 97_1〇〇, whose title is " Endpoint Detection by Chemical Reactions " It is incorporated herein by reference in its entirety. Ming Fan I :::: For semiconductor plus and more specifically, 'is for the detection of the end point of a thin film that is less overlaid on another film. The invention is thin: Physical: On the integrated circuit An important step in manufacturing is the selective formation and removal of 10,000 substrates. These films are made with the title "borrowed and its title is" gaseous (Please read the precautions on the back first ¾ fill out this Page) Its title is, and borrowed its title is, and borrowed rl installed -------- Order --------- #

Paper size turning (eNS) A4-(2_f 297 mm) ^ 57356 A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557356

An exception to this is U.S. Patent 5,399,234, issued to Yu et al., Which describes a chemical reaction between the hydroxide in the polishing slurry and the layer to be polished. The polishing end point is monitored by transmitting sound waves through the slurry and detecting changes in the speed of sound, because when the polishing barrier layer below it is reached, the concentration of reaction products from the layer to be polished (in the case of polishing silicon dioxide, Presumably silanol) will decrease. Each of these prior art methods has inherent disadvantages, such as the inability to monitor immediately, the wafer must be removed from the processing device to check whether the polishing is complete (not on the spot), or lack of sensitivity. These shortcomings have been overcome using the on-site endpoint detection system for conductive films, such as described in US Patent 5,559,428 issued to Li et al., Entitled "On-Site Monitoring of Changes in Film Thickness", but non-conductive The proper endpoint detection of the film is yet to be described. Therefore, there is still a need for a spot, real-time endpoint detection system applicable to all types of films. Such a system should have high detection sensitivity and extremely fast response time, which is better It is less than 1 or 2 seconds. SUMMARY OF THE INVENTION Therefore, one item of the present invention is to provide a method and device for detecting the removal end point of any type of film covered on another film. Another aspect of the present invention The project is to provide on-the-spot endpoint detection when the film is being removed. Tian also aims to provide endpoint detection with high detection sensitivity and extremely fast response time. It is not as good as the others listed above. Purpose 'describes a method for detecting coverage block

This New Rule Money @National Standard (CNS) A4 Specification (2Ϊ〇 X 297mm) 557356

V. Description of the invention (4) The method of removing the end of the target film on the printed film produced by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the method is to use-a kind of ^ and the barrier film and the target film-selective The reaction product < manufactures privately and removes the target film; ⑼ converts the chemical reaction product into individual products; and ⑻ monitors the content of the individual product when the target film is removed. It also describes a method of detecting the coverage of the barrier film. Method for removing the end point of the target film. One of the target film and the barrier film includes a nitride. The method is as follows: (a) using a system that produces ammonia when the nitride is exposed to the process, and the target film is removed; ⑼ convert the ammonia into individual products; and (c) monitor the ammonia content when the target film is removed. The present invention describes another method for detecting the target film covering the barrier film < removal end point The method is to use a process that will selectively produce gaseous chemical reaction products with the barrier film and the film of k, remove the target film, and (b) make the existing gaseous chemical reaction produce Mixed with individual gases to form solid particles, and (c) monitoring the solid particles when the target film is removed f ° also describes a method for detecting very low concentrations of substances in a liquid by extracting the substances present in the liquid Become a gas, mix this gas with another substance to form solid particles, and monitor the solid particles to measure the substance. The present invention describes another method for detecting the end point of the exclusion of the target film covering the barrier film. The method is to (a) use a process that produces a chemical reaction product with the barrier film to remove the target film; and monitor the content of the chemical reaction product when the target film is removed. Also describe a method for detecting the resistance of the overlay industry The method of removing the end point of the target film on the film, the target film: one of the barrier films and the barrier film contains nitride, the method is to use a kind of equipment, install -------- order ---- -(Please read the notes on the back before filling this page)

557356 A7 V. Description of the invention (5) When the nitride is exposed to the manufacturing process, ammonia is produced, and the target film is removed; and (b) when the target film is removed, the ammonia content is monitored. A method for detecting a substance at a very low concentration in a liquid is also described by extracting a substance existing in the liquid into a gas. The method includes contacting a first side of a hydrophobic permeable film with a liquid containing the substance, so that The second side of the film is in contact with the airflow and allows the substance to pass through the film as a gas and becomes transported in the airflow, and the airflow is monitored to detect the substance. It also describes another method for detecting the end point of the removal of the target film overlaid on the barrier film. The method is to use a slurry for chemical and mechanical polishing. By (a) using a process that produces a chemical reaction product in the slurry, The target film is removed, (b) a reagent that produces characteristic results when reacted with a chemical reaction product is added to the slurry, and (c) the characteristic results of the slurry are monitored when the target film is removed. Also described is another process for reducing the amount of gaseous products in solution by contacting the first side of the hydrophobic film with the solution, bringing the second side of the hydrophobic film into contact with the aqueous liquid stream, and allowing the gaseous product to pass gas It passes through the membrane and becomes transported in an aqueous stream. It also describes another method for detecting the end point I of the target film covering the barrier film. The method is as follows: ⑻ Use a process that selectively produces a chemical reaction product with one of the barrier film and the target film, and remove the target film. '(B) convert the chemical reaction product into an individual product; (c) generate an excited species from the individual product; and, when the target film is removed, monitor the amount of light emitted by the excited species. Describes the removal of another target film that covers the barrier film. This paper size is based on the CNS A4 specification. Note: -8-X 29 ~ Γ (published) 557356 A7 B7 V. Invention (6) The method of describing the end point is to use a process that selectively generates a gaseous chemical reaction product with one of the barrier film and the target film, and remove the target film; and when the target film is removed, the lower limit photoionization is used. Mass spectrometry, measuring the content of chemical reaction products with age. BRIEF DESCRIPTION OF THE DRAWINGS These and other features, aspects, and advantages will be more apparent and clearer from the detailed description of the invention below, where: Figure 1 shows a cross-section of a target film to be chemically-mechanically polished; Figure 1A shows an enlarged view of the polished substrate shown in Figure 1; Figure 2 shows a cross-section of an ammonia scrubber to reduce the ammonia concentration in the slurry before polishing; Figure 3 shows a device for slurry sampling and ammonia detection using reagents Figure 4 shows a cross-section of an extraction unit for extracting ammonia from a slurry; Figure 5 shows a device for detecting ammonia using light scattering; Figure 6 shows an enlarged view of monitoring in Figure 5; Figure 7 shows the conversion of ammonia into NO and Device using mass spectrum detection; Figure 8 shows a NO sampling device using resonance-enhanced multiphoton ionization spectroscopy (please read the note on the back first @ write this page) Φ rl 装 # Printed by the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Fig. 9 shows a device for converting ammonia gas into NO and using chemiluminescence detection; Fig. 10 shows a computer monitor output trace of semiconductor wafer polishing; Fig. 11 shows chemical detection using Fourier transform microwave spectroscopy The detection device; and FIG. 12 shows a chemical detection device using low-limit photoionization mass spectroscopy; all according to the present invention. ___________-9-This paper has been used in accordance with the Chinese National Standard (CNS) A4 specification ⑵〇χ 297 公 爱) — ， Invention description (7) Description of the silk fish body embodiment The present invention is only related to chemical_mechanical polishing Explained as a specific example, rather than limiting the applicability of the present invention to semiconductor technology. Those skilled in the art will appreciate that the present invention can be widely applied to any process in which it is desired to detect the end point of the removal of the target film overlaid on the barrier film by using a method that includes the following steps: One of the film and the target film is a process for selectively generating chemical reaction products to remove the target film; (b) converting existing chemical reaction products into individual products; and monitoring the content of individual products when the target film is removed; or By a method including the following steps, (i) using a process that selectively generates a gaseous chemical reaction product with one of the barrier film and the target film, removing the target film, (b) mixing the existing gaseous chemical reaction product with an individual gas, To form solid particles, and (c) monitor the amount of solid particles when the target film is removed; or, by a method that includes the following steps, using a process that produces a chemical reaction product with the barrier film, remove the target film ; And (b) when the target film is removed, monitoring the content of the chemical reaction products; or by chemical mechanical polishing, using a slurry, By a method including the following steps, (a) using a process that generates a chemical reaction product in the slurry, removing the target film, (b) adding a reagent that will produce a characteristic result when reacting with the chemical reaction product, In the slurry, and (c) when the target film is removed, measure the characteristic results of the slurry; or, by a method including the following steps, (a) use a chemical that selectively produces one of the barrier films and one of the films The process of the reaction product, remove the target ^ V. Description of the invention (8) A > () to transform the reaction product into individual products; to produce species from individual products, and when the target film is removed, Monitor the light content emitted by the excited species; or, by using the following steps, use a process that selectively produces a gaseous chemical reaction product with one of the trapping film and the target film, and remove the target film; (B) When the target film is removed, the content of the chemical reaction product is monitored by the low-limit photoionization mass spectrum. The present invention is also directed to a reduction in the amount of gaseous products in a solution, and more specifically to a low level of yak in a gaseous product in a polishing slurry used in chemical and mechanical polishing. Those skilled in the art will understand that the present invention can be widely applied to any process in which it is desired to reduce the amount of gaseous products in a solution by contacting the first side of the hydrophobic film with the solution and making the second one of the hydrophobic film The sides are in contact with the aqueous liquid stream 'and allow gaseous products to pass through the membrane as a gas and become transported in the aqueous liquid stream. The present invention is also widely applicable to any process in which it is desired to detect the end point of the removal of a target film overlaid on a barrier film. One of the target film and the barrier film contains a nitride. When the nitride is exposed to a process that produces ammonia, the target film is removed; (b) the existing ammonia is converted into individual products; and (c) the ammonia content is monitored when the target film is removed. As shown in FIG. 1, we have found that when a substrate 100 is chemically-mechanically polished using a slurry 'containing potassium hydroxide (KOH), the substrate has an oxide (SiO 2) thin film 1. 4-position on the nitride (Si3N4) barrier film 102, when it reaches the interface 106, a chemical reaction will occur, resulting in the production of ammonia (nh3). -11-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Produced by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. More specifically, the slurry used was fumed silica, water, and mixtures thereof, having a pH of about 105. When polishing oxides, the following reactions occur:

Si02 + 2 KOH + H2〇-> K2Si03 + 2 H20 When nitride is polished, the following reactions occur:

Si3 N4 + 6 KOH + 3 Η 2 Ο 3 K2 Si03 + 4 NH3 dissolves the generated ammonia in the slurry, and due to its relatively high impotence, it exists mainly in the form of NH3 rather than NH. Therefore, the change in the ammonia content in the slurry means that the nitride film below it has been reached and the end point of removing the oxide film can be measured by monitoring the ammonia content in the slurry. Once you reach the end point, you can stop polishing. More generally, T, the end point of removing any non-nitride-containing film covering the nitride-containing film can be detected by monitoring the ammonia content in the slurry. Conversely, the end point of removing the nitride-containing film covering the non-nitride-containing film can also be detected in a similar manner, in which ammonia is present initially, and a significant decrease in the amount of ammonia indicates its end point. And more generally, when one component of the slurry selectively reacts with one of the films (the film covered on or under it), removing the end point of any film covered on the other film can Detected by monitoring the content of chemical reaction products in the slurry. The above reaction that produces ammonia will be discussed below, but is not intended to limit the scope of the invention to this particular embodiment. In order to achieve the above findings regarding the production of ammonia in an environment suitable for manufacturing, it is necessary to collect the slurry and sample it on the spot (meaning when the wafer is being polished). Collection and I-12-This paper size applies to China National Standard (CNS) A4 specification ⑵Q χ 297 public love)

.. ------ (Please read ^ J on the back to write this page first) 1111111. 557356 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1〇) Sampling is better Provides fast response with high sensitivity (for ammonia) and minimizes interference from other substances in the slurry and ambient air. Unfortunately, the above-mentioned slurry already contained ammonia D before being used for polishing. The ammonia concentration changed from as low as 5.0 × 1CT 6 Molar concentration (M) to as high as 5.0 × 10-5 M. When polishing the coating (meaning uniform) layer of nitride, the ammonia produced in the slurry is about 1.0 × 1 (Γ4M at room temperature; for 15% wafer area (the rest is oxide)) The typical low pattern factor of the nitride layer for manufacturing wafers and polishing at the oxide / (oxide + nitride) interface will produce 1.5 X ΚΓ 5 Μ. In this case, the desired concentration change will not It can be distinguished from the fluctuation of polishing gas concentration during polishing. Therefore, the ammonia concentration before polishing this type of wafer must be reduced to achieve the required sensitivity. The ammonia concentration before polishing can be reduced if necessary by using an ammonia scrubber. In the above case, the scrubber will reduce its concentration to about 2.5 X 1 (T6M. The main component of this scrubber is the Liqui-Cel membrane contactor 200 (Extra-Flow 4x28 type, by

Hoechst Celanese), shown in Figure 2. This contactor contains Celgard (TM) microporous polypropylene fiber 202, which is hydrophobic and does not allow aqueous solutions to penetrate the fiber membrane, but does allow gas exchange. The slurry from the storage tank enters the contactor 200 at 204 and flows through the contactor 200 on the outside of the fiber (also known as the shell side), allowing ammonia to penetrate into the inside of the fiber (also known as the cavity side), and then Leave at 206 and recycle back to 204. To help remove ammonia from the slurry, an HC1 aqueous solution with a pH of about 3 from another storage tank was circulated in the cavity side, entered at 208, departed at 21 °, and then recycled back to 208. From the slurry and hybrids enter this Ηα air flow -------------- install -------- order --------- (Please read the precautions on the back before Fill out this page) -13- 557356 A7 V. Description of the invention (The ammonia gas in 11 is immediately converted into NH4 + by a moderately high concentration of protons, so it is effective to prevent the possibility of any small amount of NH3 in the scrubber cavity side Accumulation. This recycled aqueous HC1 liquid stream and storage tank can then be a drainage tank for a large amount of ammonia from the slurry. Use an aqueous HC1 storage tank with about 10 liters of water and adjust to ρΗ3.5 with 0.1 M HC1 solution, and Let 10 liters of impotence pass through the contactor with ... ammonia solution, then within 30 minutes, reduce the ammonia content to the required 25 × 10_6M. This time can be reduced by increasing the contactor Size, use several contactors in series' or gently heat the slurry to increase the volatility of ammonia, or any combination of these three methods. The desired ammonia content in the slurry can be measured by commercially available detectors, such as Ammonia-specific ion-selective electrode (ISE). Once the slurry has reached the required ammonia content, use it immediately The wafer is then polished. The slurry is then collected from the polishing pad for sampling during the polishing process. This slurry may be analyzed with appropriate reagents as appropriate to indicate the presence or absence of chemical reaction products. The staff is to detect liquid ammonia (in color) in the slurry Milky white), a suitable option is to use Nessler reagent (basic solution of potassium iodidemercurate), which will turn into a characteristic brown when reacted with ammonia. After the wafer is polished, it comes from polishing 8108 (Refer to Figure 1 & 3) The slurry 300 at the previous point was sent continuously through the inlet valve 301 to the storage tank 300. The Nessler reagent 304 was pulsed to the storage tank 302. The opening 306 in the slot 302 is used to discharge the slurry ^ the reagent mixture to a waste container (not shown). The valve 3001 and the opening 3006 are adjusted so that the slurry can be achieved and maintained in storage The dynamic balance in the tank 30. More specifically, the slurry continuously flows into the storage tank and is continuously discharged, and there is still -14- # This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Love) 557356 V. Description of invention (12) New enough The slurry stays in the storage tank to achieve the purpose of detecting ammonia. The storage tank 302 has at least one wall or a part of the wall 308 is transparent. A color sensor 310 (commercially available) is placed in the storage tank. The transparent part of the tank 300 is outside the 308, and when the Nessler reagent reacts with any ammonia in the slurry, it will change color. This method can reduce the concentration to 5 x 10-6 Molar (about 100). Ammonia is detected at a concentration of tritium, where the color change occurs in less than J seconds. Once a characteristic color change is found, the nitride layer is exposed and the polishing is stopped as needed (polishing can continue for a certain period of time in this industry Called, over-polished "). A computer can be installed to control the process, a signal can be obtained from the color sensor, and the signal can be passed back to the polisher to stop polishing. It should also be noted that other reagents can be used for endpoint detection, depending on the chemical reaction products generated during the film removal process. In general, reagents added to the slurry will cause reactions that produce characteristic results, such as color changes, photons (meaning, the emitted light), or precipitates. Examples of equipment used to detect feature results have been described in the context of color changes. To detect photons, a suitable sensor is used, such as a conventional photoelectric = multiplier or infrared sensor. In order to detect the sediment, a light scattering device can be used. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1 Sampling square hair of ammonia dissolved in the slurry. Once the slurry is collected from the polishing pad, various sampling methods can be used. A representative methodology is described below. Ion-selective electrode A method for detecting liquid ammonia. It uses a commercially available ion-selective electrode 'with an internal electrode solution of a specific pH ，, which is of great interest to us ... I-15- This paper is applicable to China Standard (CNS) A4 size (210 X 297 mm) 557356

、 Explanation of invention (13 The solution printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a fun solution, which was contacted by a semi-permeable hydrophobic film. This film allows ammonia gas from the slurry to pass through, changing the impotence of the internal electrode solution. Electrochemical monitoring. This method can detect ammonia down to 5xl0_7 Molar concentration I, which is less than 30 seconds at high concentrations, but it can take up to 1-3 minutes at low concentrations. It is suitable for many applications, However, it is not suitable for the detection of this specific CMP endpoint. Fluorometric measurement Another way to detect ammonia in the liquid phase is to use a composite reagent that will impart fluorescent species when contacted with ammonia. The reagent contains phthalic acid (OPA) and a sulfite that acts as a reducing agent (see z. Genfa et al., &Quot; Measurement of Fluorine in Water-Injected Ions in a Flow Injection System ", such as chem, Volume 61, Page 408, 1989). The reaction products are highly fluorescent and can be detected using emission spectroscopy at concentrations down to 2x10_8 Molar. However, this method can take up to 10 minutes, Can reach To the full, it is not suitable for this CMP application again. The measure of chemiluminescence due to the reaction of ammonia with hypobromite in the test solution has also been performed using a photomultiplier tube with an amplifier (see also others etc. People, using flow injection analysis and chemiluminescence analysis to determine ammonium ions in rain and fog water, Anal Chem., Vol. 65, p. 3489, I " 3). However, this method does not have all The sensitivity required to monitor the ammonia produced during CMP polishing of nitrides in this application. The response time of this method is too slow to provide on-the-spot real-time program control. Ammonia gas extraction from slurry _____ -16- This paper has been used in China National Standard (CNS) A4 specification ⑵G x 297 Public Love 1 '— · 1— (Please read the precautions on the back @ write this page first) — — — — # 557356 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (14 is for detecting and monitoring ammonia in the form of gas, so that methods such as mass spectrum can be used, so it will come from the polishing device. (Not shown) The slurry is pumped through the ammonia extraction unit 300 shown in Fig. 4. The extraction unit 300 is composed of polypropylene microporous hollow fiber 302, which is obtained from a Liqui-Cel contactor (type 2.5x8, removed by Hoechst) Made by Celanese). Fiber 302 allows gas but does not allow liquid to pass from the outside to the inside of the fiber. The slurry is pumped in at 304, passes through extraction unit 300 on the outside of fiber 302, and leaves at 306. Dry and clean The gas (from a dryer containing an ammonia filter and optionally a NOx filter to remove it) is pumped into 308 through the fiber and exits at 310 with a gas stream 312 containing ammonia. The carrier gas is pumped at a reduced pressure of about 30 Torr to help the ammonia be transported from the slurry through the fibers and into the gas stream. Decompression also increases the overall flow rate, which helps reduce response time to measure changes in ammonia concentration. The ammonia-containing gas stream 312 obtained from the extractor 300 can then be analyzed and the end point detection of the target film removed can be monitored. Gas-phase chemical analysis, such as standard mass spectrometry, can be sensitive to the south and has a fast response time, which is desirable for endpoint detection. However, as the slurry is sampled, there is substantial interference from water vapor, which, although only higher by 1 atomic mass unit (AMU), is abundantly present. During electron impact ionization, water mass 18 may lose one chlorine, resulting in a 0Η ion with mass 17, which has the same mass as NΗ; 3+. Therefore, the ammonia signal from the slurry can be masked very effectively, so endpoint detection becomes impossible. After light scattering in ammonia gas has been extracted from the slurry, it can be mixed with hydrochloric acid vapor. 17- Sheet paper standard (CNS) A4 specification (210X 297 mm) (Please read the notes on the back first and fill in (This page) rl ^ y ^ — I ----- Order --------- # · 557356 Printed Agriculture A7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ______B7 _ V. Description of Invention (15), and Monitor the formation of ammonium chloride solid particles for detection according to the following reaction formula: NH3 (g) + HC1 (g) + nH2 0 NH4 C1 (H2 0) n (s) The device used for this monitoring system is Shown in Figure 5. The ammonia-containing gas stream 312 from Fig. 4 is mixed with a gas stream 402 containing a known concentration of gaseous HC1 and having a well-controlled humidity. Upon mixing, ammonia and hydrochloric acid vapor react immediately to form solid ammonium chloride particles 404. The amount of ammonium gaseous gas produced is measured using a laser beam 406, such as a helium-neon laser, by monitoring the macroscopic scattering obtained from the particles 404. Figure 6 illustrates how to monitor scattering. The scattered photons that strike the particles 404 by the laser beam 406 are detected by the photomultiplier tube 502. It is preferred to use a narrative collection system 504 'to improve the efficiency of the southern light collection. The sensitivity of this technique can be achieved using a mechanical stop 408 (such as the Stanford Research System Model SR450) in Figure 5 and a lock-in amplifier (not shown; for example, Stanford) synchronized with an interrupter that provides phase sensitivity Research system SR810). When the wafer is being polished, the amount of scattered light is directly proportional to the ammonia concentration in the slurry. This reaction to form solid particles is very fast because it is a simple acid-test reaction and is selective for ammonia. , Because very few gas molecules behave like experiments. This reaction occurs in less than 1 second, and it is very suitable for the endpoint detection system as described. It should be noted that the light scattering methods and devices described are not limited to use with monitoring CMP endpoints. If the film overlying is removed from the film underneath, such as dry etching (such as reactive ion etching), then the lower -18- This paper size applies to the national standard (CNS) A4 size ⑽ x 297 ) — ~ ^ _ .---- ^ -------- ^ ---------. (Please read the notes on the back to write this page) 557356 A7 B7__ — V. Invention Note (16) The square film (meaning the barrier layer in the last name) may be selected to produce a marked chemical reaction product when in contact with the etchant. The reaction products of the etching process can be sampled by the method described above to monitor the content of the labeled chemical reaction products. This light scattering method can also be used to detect substances in liquids at very low concentrations (such as 丨 〇χ 〇-5m or lower), such as ammonia, by extracting chemical substances in gaseous form from the liquid, so that This gas is mixed with another substance to form solid particles, and the amount of solid particles is monitored, for example by scattering light. Transformed into nitric oxide (1) The interference of 0H of water fragments can be avoided by converting the ammonia in the ammonia-containing gas stream from the extraction unit 300 (shown in Figure 4) into individual products with different masses than 0H, and By detecting the individual products, ammonia is detected indirectly. One example is the use of a catalyst converter as shown in Figure 7 to convert ammonia to nitric oxide (NO). The ammonia-containing gas stream 312 enters the catalyst converter 400, such as an array of stainless steel pipe parts, which has a large enough surface area for a sufficient amount of gas to be converted. The system is heated to 800C. This conversion, called the Oswald process, is illustrated by the following reaction: 4 NH3 (g) + 5 02 (g) — 4 NO (g) + 6 Η 2 Ο (g) It should be noted that the The carrier gas preferably contains oxygen (02) instead of air, because air contains about 15 ppm and a nitrogen isotope (7N15) 2 of mass 30, which is the same mass as NO. Mass spectrum The gas stream 402 exiting the converter 400 contains NO and enters the mass spectrometer system 404. The bypass valve 406 is used to adjust the flow of the airflow and allows substantial adjustment (please read the note on the back? Matters @ write this page) rl installation ---- order --------- Ministry of Economics wisdom Printed by the Consumers ’Cooperative of the Property Bureau μ® National Standard (CNS) A4 Specification (21G χ 297 Public Love)-557356 A7 B7 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (17) Body Flow through Extraction Unit 300 and catalyst converter 400, resulting in a fast measurement of response time without overloading the mass spectrometer 404 with the incoming sampling gas containing NO gas. The mass spectrometer system 404 includes a hollow chamber 408, which contains a quadrupole mass spectrometer, and collides with an ionization source 410, such as the Stanford Research System Residual Gas Analyzer RGA200. This mass spectrometer has a dynamic range of eight orders of magnitude and can detect NO down to about 10 ppb. This mass spectrometer is gated to detect ions only at mass / charge 30, and the signal is available on a computer to provide real-time monitoring. REMPI-TOF Mass Spectroscopy An alternative to mass spectroscopy is resonance enhanced multi-photon ionization (REMPI) spectroscopy, which has been described as true and easy to detect the presence of nitric oxide (see DC Jacobs et al.) Human, "1 + 1 resonance enhanced MPI spectrum reduction to cluster distribution: application to the NO Α2 Σ + _ χ2Π system", J. Chem. Phys. Vol. 85, p. 5469 (1986). In Figure 8 In the process, the NO-containing gas stream 402 leaving the converter 400 passes through the bypass valve 502 similar to that described above and enters the time-of-flight (TOF) mass spectrometer 500. The pulse molecular beam valve 504 transforms the gas stream 402 into a pulsed gas stream 506. The pressure of the gas stream 402 is about 30 Torr, which is sufficient to form a beam when entering the chamber of the spectrometer, but may not expand at a supersonic temperature. The pulse valve 504 is timed to coordinate with the pulsed laser beam 508, which is Selectively ionize NO from the pulsed gas stream 506. The laser beam 508 can be, for example, the output of a laser system with a frequency-doubling Q-converted Nd: YAG laser that operates at 20 Hz to pump titanium Sapphire (Ti: S) tunable laser. Ti: S laser system It is rounded to 904 nanometers, and its output is doubled by using a BBO nonlinear crystal. The second harmonic is at 452 nanometers, and the fourth -20- This paper size applies to China National Standard (CNS) A4 specifications. (210 X 297 mm) (Please read the notes on the back @write this page first) Binding ---- Order --------- # 557356 A7 -------- R7______ V. Invention It shows that (18) harmonics are at the desired wavelength of 226 nm, or are excited by photons of NO from one of the ground states. The ionization system described has proved extremely effective, in which the total detection sensitivity is reduced to 1.0 × 10 -11 Torr (see M. Asscher et al., “Vibration and rotation energy distribution of NO scattered from the surface of Pt (in) crystal: detection by two-photon ionization”, Phys Rev. Lett Vol. 49, Page 982. The pulse ionizing gas flow 506 is then accelerated by using the electric field generated by the electrode 51. The plasma travels through the length of the drift tube 512 to the detector 514. The running time of the ion is determined by its mass. Proportional, and therefore the time gating of the arrival signal, is only used to measure the signal from N0. The resulting signal is Boxcar averager 516 (available from Stanford System Model SR250) to 'average' and direct to computer for processing (not shown). Based on static gas measurement 'expects this technology to have a sensitivity of 10 ppb and response time Conversion to Nitric Oxide The ammonia in the ammonia-containing gas stream obtained from the extraction unit 300 (shown in Figure 3) is converted into individual products, and by detecting individual products, ammonia is detected indirectly. One example is the use of a catalyst converter as shown in Figure 9 to convert ammonia to nitrogen monoxide (NO). The ammonia-containing gas stream 312 enters the catalyst converter 400, such as an array of stainless steel pipe parts, which has a surface area large enough for a sufficient amount of ammonia molecules to be transformed, and it is heated to 800 ° C. This conversion, called the oswajd process, is illustrated by the following reaction: 4 NH3 (g) + 5 02 (g) ^ 4 NO (g) + 6 H20 (g) The carrier gas should be dry and clean, so it can achieve rapid Response time and the most -21-This paper size applies Chinese National Standard (CNS) A4 specification (21G x 2W public director) '-' '' (Please read the precautions on the back first to write this page) r; 丨 装 # · Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives 557356 A7 B7__ V. Description of the invention (19) Low (background NO. The conversion of NO plus N0 is measured by chemiluminescence, which enables detection at sub-ppb levels and avoids Interference from other chemicals. Chemiluminescence detection (CLD) The phenomenon of chemiluminescence occurs when an excited molecule 'generated from a chemical reaction shifts from an excited state to a lower state that allows it to emit light. Chemiluminescence can be used to Detect the presence of ammonia (indirectly by detecting nitric oxide), in this case according to the following formula: N〇 (g) + 〇3 (g) no2 * (g) + o2 N02 * (g) —N 〇2 (g) + hv where the emitted light (photons) is detected by a highly sensitive photomultiplier tube (ρΜχ) The device used for chemiluminescence detection (CLD) is shown in Figure 9. The NO-containing gas stream 402 leaving the converter 400 passes through the flow limiter 406, enters the chemiluminescence detector 404, and is mixed with ozone in the reaction chamber. Ozone is generated by a conventional ozone generator, as shown, with a flow limiter 408. In reaction 1, 'NO' and 〇3 are reacted as described above to produce stimulated molecules of No2 *, which will emit broadly. The light of the band is centered at 1200 nanometers. A very sensitive PMT 410 (e.g., detector from ECrich Physical Instrument Company (Zurich, SwitZerland)) detects emission through a color filter, which is used for In order to exclude photons with undesired wavelengths, PMT 410 operates in photon calculation mode and is controlled and processed by signal conditioner 412. The signal is then stored in computer 414, which is monitored] ^ 〇2 * Chemiluminescence signal, And use the output ^ Connect to a polishing machine (not shown) to control the polishing process. (Please read the precautions on the back to write this page) -------- Order --------- Ministry of Economy Printed by the Intellectual Property Bureau Staff Consumer Cooperatives-22- 557356 A7

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I. 557356 A7 B7 V. Description of the invention (21) Fourier transform microwave spectroscopy using pulsed gas phase injection has extremely high detection sensitivity and chemical selectivity, and can accurately measure pollutants at sub-ppb levels And overcome the shadowing problems associated with mass spectroscopy (see Harmony et al., "Small Thermal Nozzle Fourier Transform Microwave Spectrometer", Rev. Sci. Instrum., Vol. 66, p. 5196 (1995), and Suenram et al. People, “Effect of Turner Movement on the Quadrupole Ultrafine Structure of Cultivation”, J. Mol. Spectrosc., Vol. 137, p. 127 (1989)). Ammonia-containing gas stream 312 from extractor 300 ( (Shown in Figure 4) is directed to the Fourier Transformed Microwave Spectrometer 400, shown in Figure 11. Bypass valve 402 is used to adjust the flow of gas into the pulse valve 404. Bypass valve 402 allows substantially whole flow through the extraction unit 300 This results in a quick measurement of the response time without overloading the spectrometer 400 with the sampling gas of the incoming ammonia-containing air stream. The pulse valve 404 injects the sample gas from the gas stream 312 into the empty chamber of the spectrometer, where the repetition rate is about 20 Hz, and the valve opening time is 1 millisecond. The pulsed gas enters the chamber and expands at supersonic speed, so it cools down to about 10 degrees K. High intensity microwave radiation (23.786 GHz for ammonia) is also pulsed at 20 Hz (after The timing is in accordance with the pulsed gas) into the chamber, from the microwave source 406 to the transmitter / receiver 408. The ammonia molecules absorb the radiation and re-radiate it in a free induction decay process. The decay is then digitized by the detector 410 And transform to obtain a frequency-domain signal. Monitor the intensity of the signal to determine the amount of ammonia present in the slurry. Low-limit photoionization mass spectrum In this method, the low-limit photoionization of ammonia is used and then analyzed by fourth-order mass spectrometry Detector detection, as shown in Figure 12. Leave the extractor 300 shown in Figure 4 _-24-_ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back first (Precautions written on this page) Outfitting -------- Order --------- #. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557356 A7 B7 Employees’ Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printing V. Ammonia-containing gas flow 312 of invention description (22), It is guided through the bypass valve 502 to the photoionization mass spectrometer 500 (for example, Syagen technology TPMS-100S). The sample area 504 at a pressure close to 1 Torr is illuminated by a chirped resonance lamp 506, which has two The main hollow UV strips are at 10.0 eV and 10.6 eV. The lines at 10.6 eV are slightly higher than the ammonia ionization potential (IP) 10.18 eV, and just below the water ip < at 12.6 eV). Due to the ions formed by the irradiation, they are guided through the small aperture, into the high-air chamber 508, and detected by a modified quadrupole mass spectrometer 51. This mass analysis is used to distinguish interference from hydrocarbon species with low ionization potential, which can be easily ionized by krypton lamps. Expect a detection sensitivity of better than 10 ppb. The additional advantage of using photoionization instead of the more conventional electron impact ionization is that to prevent water fragmentation, water fragmentation will cause fragment ions (OH) with a mass of 17, which is the same mass as ammonia. In addition, this photon energy is lower than the ionization potential of other gas molecules that may exist, including N2, 02, C02, CO, and most importantly H20. It should be noted that the low-limit photoionization mass spectrum and Fourier transform microwave spectroscopy, methods, and devices are not limited to use with monitoring CMP endpoints. If the overlying film is removed by etching from the underlying film, such as dry etching (such as reactive ion etching), the underlying film (meaning the etch barrier layer) can be selected to produce a contact with the etchant. Those who mark chemical reaction products. The reaction products of the etching process can be sampled by any of these methods to monitor the content of the labeled chemical reaction products. Low-limit photoionization mass spectrometry and Fourier transform microwave spectroscopy can also be used to detect substances at extremely low concentrations (such as 1.0X 10-5M or lower) in liquids. -25-

(Please read the notes on the back first to write this page) Item m Binding --------- # A7 _______B7 V. Description of the Invention (23) Quality, the chain weight is taken as g, which is extracted from the liquid Use the steps described above to detect ammonia in gaseous form. Outline > ρ From the method and related devices that can detect the removal end of any type of film overlaid on another film. The present invention provides on-the-spot end point detection when the wide film is being removed, with high detection sensitivity and fast response time at the nuclear end. &Amp; Although the present invention has been described from the perspective of a specific embodiment, the description explains that many alternatives, modifications, and variations will be familiar: obvious to the artist. Therefore, the present invention is intended to cover all such alternatives, modifications, and variations as fall within the spirit and scope of the present invention and the scope of the patents attached herewith. (Please read the notes on the back first and fill in this page) Packing ------ tr --------- # Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -26- This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

557356 "Scope of patent application: Type: Method for measuring the end point of removal of a target film covered on a barrier film, which includes the following steps: ⑻ Use-a method that will interact with the barrier film and target film-selectively generate chemistry The process of the reaction product removes the target film; ⑼ converts the existing chemical reaction products into individual products; and (c) monitors the amount of individual products when the target film is removed. Method, in which the film is removed by dry etching. 3. The method of item 2 in the patent application of Rushen No. 4, wherein the content of individual products is monitored by mass spectrum. 4. The method of item No. 2 in the patent application scope, where The content of individual products is monitored by resonance to enhance multi-photon ionization spectroscopy. 5. If the method is claimed as the first item in the patent scope, the thin film is removed by chemical-mechanical polishing. 6. If the method is applied for the fifth item in the patent scope, The chemical reaction product is contained in the slurry that has been used in chemical mechanical polishing. 7. If the method of the scope of patent application No. 6 further includes gas from the slurry Steps for extracting chemical reaction products. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 8. If the method of patent application No. 7 is applied, the extraction step includes: contacting the first side of the hydrophobic film with the slurry; making hydrophobic The second side of the film is in contact with the gas stream; and allows the chemical reaction products to pass through the film as a gas and become transported in the gas stream. 9. The method of the first item of the patent application park, wherein the conversion step uses a contact Paper size applies to China National Standard (CNS) A4 (210X297 mm) 557356 A8 B8 C8 D8 Scope of patent application Media conversion. 10_ The method in item 8 of the patent scope of claim 4, wherein the content of individual products is monitored by mass spectrum. 11. The method according to item 8 of the patent application park, wherein the content of individual products is enhanced by resonance-monitored multiphoton ionization spectroscopy. U The method of claim 1 in the patent application scope further includes the step of stopping the removal process when the end point has been reached. 13. A method for detecting an end point of removal of a target film covering a barrier film, one of the target film and the barrier film contains a nitride, and the package includes the following steps: (a) using a nitride A process that produces ammonia when exposed to the process removes the target film; (b) converts ammonia to individual products; and monitors the amount of ammonia when the target film is removed. K is the method according to item 13 of the patent application, wherein the individual product is nitrogen oxide. 15. The method according to item μ in the scope of patent application, wherein the step of Ding Dehua uses a catalyst converter. 16. The method of claim 13 in which the thin film is removed by chemical and mechanical polishing. Π · The method of applying for the first item in the patent application, in which the 袅 open τ wind system is contained in the slurry which has been used for chemical mechanical polishing. 18. The method according to item 17 of the patent application, further comprising the step of extracting ammonia from the slurry by gas. -28-This paper size applies to Chinese National Standard (CNS) Α4 size (210 X 297 mm) (Please read the notes on the back before filling out this page} Order-d Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 557356 A8 B8 C8 D8 Patent Application 19. The method of claim 18, wherein the extraction step includes: contacting the first side of the hydrophobic film with the slurry; contacting the second side of the 4 water-based film with the air stream; and Ammonia is allowed to pass through the membrane as a gas and becomes transported in a gas stream. 20. The method of claim 13 in the scope of patent application further includes the step of 'stopping the removal process when the end point has been reached. 21. The scope of claim 13 in the scope of patent application Method, wherein the nitride is in the barrier film. 22. The method according to item 21 of the patent application, wherein the content of the chemical reaction product will increase when the target film is removed. 23. If item 13 of the patent application is applied Method, wherein the nitride is in the target film. 24. The method as claimed in item 23 of the patent application, wherein when the target film is removed, the chemical reaction is The content of the product will be reduced. 25 · —A device for detecting the end point of the removal of the target film covering the barrier film 'is a process that selectively generates a chemical reaction product with one of the barrier film and the target film, The device includes: a converter for converting a chemical reaction product into an individual product; and a monitor for monitoring the content of the individual product when the target film is removed. 26. The device according to item 25 of the patent application, wherein the The process is chemical and mechanical polishing using a polishing slurry, and the ammonia system is included in the polishing slurry, which further includes an extractor for extracting chemical reaction products from the slurry with gas. 27. The device according to item 26 of the scope of patent application , Where the extractor includes: ------ -29- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page}-Order economy Printed by the Employees 'Cooperatives of the Ministry of Intellectual Property Bureau Printed by the Consumers' Cooperatives of the Ministry of Economics and Intellectual Property Bureau 557356 A8 B8 C8 ______ D8 6. Scope of Patent Application The arrangement in which the first side of the hydrophobic film is in contact with the slurry; the arrangement in which the second side of the hydrophobic film is in contact with the air stream; and the setting that allows the noon chemical reaction product to pass through the film with the gas and becomes the arrangement to be transported in the air stream. 28. If the device is claimed as item 27 of the patent scope, the extractor includes a contactor, which contains microporous fibers. 29. The device as claimed in claim 25, wherein the monitor includes a mass spectrometer. For example, the device is called the Patent Fanyuan Item 25, wherein the monitor includes a resonance enhanced multi-photon ionization spectrometer. 31. The device as claimed in claim 25, wherein the converter includes a catalyst converter. 32. A method for detecting an end point of removal of a target film overlaid on a barrier film, comprising the following steps: ⑻ & using a process that selectively generates a gaseous chemical reaction product with one of the barrier film and the target film, Remove the target film; (i) mix the presence of the gaseous chemical reaction product with individual gases to form solid particles; and (c) monitor the amount of solid particles when the target film is removed. The method of the patent application scope item 32 is as follows, in which the film is removed by drying. 34 ·: The method of item 33 of the Qing patent scope, wherein the content of the chemical reaction product is monitored by light scattering. 35. If the method of applying for the scope of patent No. 32, in which the film is a chemical-machine sheet and a national standard (CNS) A Dunnong (210X ^ 97 mm) '---- (Please read the precautions on the back before Fill out this page), order 557356 A8 B8 C8 D8 VI. Patent application scope Mechanical polishing removal. (Please read the precautions on the back before filling in this page) 36. For the method of applying for patent No. 35, the chemical reaction product is contained in the slurry that has been used in chemical mechanical polishing, which further includes The step of gas extraction of chemical reaction products. 37. The method of claim 36, wherein the extraction step includes: contacting the first side of the hydrophobic permeable film with the slurry; contacting the second side of the film with a gas stream; and allowing the chemical reaction product to The gas passes through the membrane and becomes carried in a gas stream. 38. The method of claim 32, wherein the monitoring step includes: contacting particles with a laser beam to produce light scattering; and measuring light scattering. 39. The method of claim 38, wherein the laser beam is generated by a helium-neon laser. 40. The method of claim 39, further comprising mechanically cutting off the scattered light. 41. The method of claim 40, further comprising locking and magnifying the scattered light. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 42. If the method in the scope of patent application No. 32, the gaseous chemical reaction product is ammonia. 43. The method according to item 42 of the patent application, wherein the individual gas is hydrochloric acid 44. The method according to item 32 of the patent application, further comprising the step of stopping the removal process when the end point has been reached. ___ -31-This paper size is applicable to China National County (CNS) A4 specification (210X297 mm) '--- printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557356 A8 B8 C8 D8 ~ 45. The method according to item 32 of the patent application park, wherein the process is to selectively generate a gaseous chemical reaction product with the barrier film. @ '46 · The method according to item 45 of the patent application scope, wherein the amount of solid particles increases when the target film is removed. 47. The method of claim 32, wherein the process is to selectively produce a gaseous chemical reaction product with the target film. τ, 48. The method according to item 47 of the patent application park, wherein the amount of solid particles is reduced when the target film is removed. 49 · A method for detecting extremely low-concentration substances in a liquid, the method of which is to extract substances existing in the liquid as a gas in the following steps; to mix the gas with another substance to form solid particles; and to monitor the solid particles To detect the substance. 50. The method of claim 49, wherein the concentration is less than or equal to 1.0 × 10-5 mole. 51. The method according to item 49 of the patent application park, wherein the extraction step includes: bringing the first side of the hydrophobic permeable film into contact with the liquid containing the substance; bringing the second side of the film into contact with the airflow Contact; and allow the substance to pass through the membrane as a gas and become transported in a gas stream. 52. The method of claim 49, wherein the monitoring step includes: contacting particles with a laser beam to produce light scattering; and measuring light scattering. 53. If the method of applying for the scope of the patent No. 52, the laser beam is based on ---.- ^ ------, can ------ (Please read the precautions on the back before filling this page ; ≫ -32- 557356 A8 B8 C8 D8 Neon laser produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to print a patent application scope. 54. If the patent application scope is 52nd Bewanwan Law, it further includes mechanical cutting. Scattered light. The method as described in page 54 of the patent application, which further includes locking and amplifying the scattered light. 56. Inhibition of debt The measurement of the removal end point of the target film covering the blocking film It is a process for selectively generating chemical reaction products with one of the barrier film and the target film. The device includes: a device for mixing the gaseous chemical reaction products and individual gases existing to form solid particles; and A monitor to monitor the amount of solid particles when removing the target film. 57. Such as the device of the scope of application for patent No. 56 'where the process is chemical-mechanical polishing using polishing slurry, and ammonia is included in the polishing slurry It further includes an extractor for extracting chemical reaction products with gas from the slurry. 58. The device of claim 57 in which the extractor includes: a device for contacting the first side of the hydrophobic film with the slurry; The arrangement of the second side of the hydrophobic film in contact with the air stream, and the arrangement that allows chemical reaction products to pass through the film with the gas, and becomes a transport in the air stream. 59. The device according to item 58 of the patent application, wherein the extractor includes The device includes microporous fibers. 60. The device according to item 56 of the patent application, wherein the monitor includes: a laser that generates scattered light from solid particles; and 33- This paper size applies Chinese National Standards (CNS) A4 specifications (210X297). ---,-^ ------ IT ------ (Please read the precautions on the back before filling out this page) 557356 A8 B8 C8 D8 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 6. The scope of the patent application measures the scattered light detector. 61. The device of the patent application No. 60, which further includes a machine for cutting off the scattered light Mechanical interrupter. 62 · :: Please apply for the patent No. 61 device, which further includes a lock-in amplifier for synchronizing the mechanical interrupter. 63 · —A device for detecting very low concentration substances in liquid, including: An extractor for extracting the existing substance as a gas from a liquid; an arrangement for mixing M gas with another substance to form solid particles; and a monitor for monitoring the amount of solid particles. * Medium concentration is less than or equal to 1.0x10-5 Molar. 65. As stated in the device in the scope of patent 63, the extractor includes: the contact between the first side of the permeable membrane and the substance containing the substance The setting; # The setting that makes the second side of the film in contact with the air flow; and the setting that allows the substance to pass through the film with gas and becomes a device that is transported in the air flow. 66. For example, the device in the scope of patent application 63, where the monitor includes : Generates a scattered light laser from a solid particle; and a detector that measures the scattered light. 67. The device of the scope of application for patent No. 66 further includes a mechanical interrupter for cutting off scattered light. Profit I: The device around item 67, the further step of which includes a step-by-step lock-in amplifier for the mechanical interruption. ----— ^ ------ 1T ------ (Please read the notes on the back before filling out this page) -34- 557356 Patent application scope A8 B8 C8 D8 Intellectual Property Bureau of the Ministry of Economic Affairs employee consumption Cooperative prints 9 · Methods to detect the end of removal of the target film overlaid on the barrier film ', which includes the following steps: Use a process that produces a chemical reaction product with the barrier film to remove the target film; Yoda removal The target film is used to monitor the content of chemical reaction products. 7Q 4 mouth, method of item 69 of the patent scope, where the film is removed by dry etching. 71. The method of claim 70, wherein the content of the chemical reaction product is monitored by Fourier transform microwave spectroscopy. 72. The method according to item 70 of the patent application park, wherein the content of the chemical reaction product is monitored by low-limit photoionization mass spectrometry. 73. The method of applying the scope of patent for silicon, wherein the thin film is removed by chemical-mechanical polishing. 74. The method of claim 73, wherein the chemical reaction product is contained in a slurry that has been used for chemical mechanical polishing. 75. The method of scope 74 of the patent application, wherein the content of the chemical reaction product is monitored by slurry sampling. % The method according to item 75 of the scope of patent application, wherein the content of the chemical reaction product is monitored by an ion selective electrode. 77. If the method according to item 74 of the scope of patent application is applied, the method further includes a step of extracting a chemical reaction product with a gas from the polymer solution. 78. The method of claim 77, wherein the extraction step includes: contacting the first side of the hydrophobic film with the slurry; contacting the second side of the hydrophobic film with the air stream; and (please read the back first Note: Please fill in this page again); equipment, 1T »35- 557356 A8 B8 C8 D8 Patent application scope Intellectual Property Bureau, Ministry of Economic Affairs, Employees' Cooperatives Printed to allow chemical reaction products to pass through the membrane with gas, and become transported in the air stream. 79. The method of claim 77, wherein the content of the gaseous chemical reaction product is monitored by Fourier transform microwave spectroscopy. 80. The method according to item 77 of the patent application range, wherein the content of the gaseous chemical reaction product is monitored by low-limit photoionization mass spectrometry. 81. The method of claim 69, further comprising the step of stopping the removal process when the end point has been reached. 82. A method for detecting the end point of a target film covering a broadcast film 'One of the target film and the trap film includes a nitride, which includes the following steps: When a nitride is exposed to a process A process that produces ammonia, removes the target film; and monitors the ammonia content when the target film is removed. 83. The method of claim 82, wherein the thin film is removed by chemical-mechanical polishing. 84. The method as claimed in item 83 of the patent application is in a slurry of chemical mechanical polishing. 85. Method according to item 84 of the scope of patent application Liquid sampling for monitoring. 86. The method according to the scope of patent application No. 84. The step of extracting ammonia by gas. 87. The method according to item 86 of the patent application, wherein ammonia is included in the used, wherein the ammonia content is by slurry, which further includes from the slurry, contacting the first side of the hydrophobic film with the slurry; wherein the extraction step includes (Please read the precautions on the back before filling out this page}; install., V " 4 557356 where the nitride is in the barrier thin when the target film is removed where the nitride is in the target thin where the target film is removed A8 B8 C8 D8 6. The scope of the patent application makes the second side of the hydrophobic film in contact with the airflow; and allows ammonia to pass through the film with the gas, and becomes transported in the airflow. 88. If the method of the 82nd application for a patent, it is further Including the step of stopping the removal process when the end point has been reached. 89 · As in the method film of the scope of patent application item 82. 90 · If the method of the scope of patent application item 89 is applied, the content of chemical reaction products will increase 91 · In the method film of the patent scope item 82. 92. If the method of the patent scope item %% is applied, the content of the chemical reaction product will be reduced by 93 ·-a kind of detection of extremely low concentration substances in the liquid Includes the following steps to extract the substance existing as a gas from the liquid, including contacting the first side of the hydrophobic permeable film with the U 恻 face and the liquid containing the substance The second side of the membrane is in contact with the gas stream; and the substance is allowed to pass through the membrane as a gas and becomes transported in the gas stream to monitor the gas stream to detect the substance. 94. For example, the method of applying for patent (ii), wherein the concentration is pure 1 0 × 10-5 Molar concentration. F ~% • As in the method of patent application No. 93, in which the monitoring step is converted to microwave spectroscopy. _-37- M's scale scale turning home standard (CNS) A4 Specifications (210 X 297 male i --------------- install -------- order -------- (Please read the phonetic on the back? Matters before Fill out this page} • Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557356 6. Scope of patent application 96. If the method of claiming patent scope item 93 is applied, the monitoring step includes low limit photoionization mass spectrometry. 97 · —A device for detecting the end point of the removal of the target film covered on the barrier film, which is a process for generating a chemical reaction product with the barrier film. The device includes: when the target film is removed, monitoring the chemistry Monitor for reaction product content. 98. The device according to item 97 of the patent application scope, wherein the process is chemical and mechanical polishing using a polishing slurry, and the reaction product is contained in the polishing slurry, and the monitor further comprises: watering the chemical reaction product in the slurry with water Sampler for form sampling. 99. The device of claim 98, wherein the sampler includes an ion-selective electrode. 100. The device according to item 97 of the patent application scope, wherein the process is chemical-mechanical polishing using a polishing slurry, and the reaction product is contained in the polishing slurry, which further includes extraction of the chemical reaction product from the slurry with a gas. Device. 101. The device according to the scope of application for patent item 100, wherein the extractor comprises: a device for contacting the first side of the hydrophobic film with the slurry; the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the second for the hydrophobic film An arrangement in which the sides are in contact with the airflow; and an arrangement that allows the chemical reaction products to pass through the membrane as a gas and become transported in the airflow. 102. The device of claim 100, wherein the monitor includes a Fourier transform microwave spectrometer. 103. For the device under the scope of patent application 100, where the monitor includes the lower limit ___- 38 -______ This paper size applies the Zhongguanjia Standard (CNS) A4 specification (210 X 297 mm 1 " 557356 Economy A8 B8 C8 ____ D8 printed by the Ministry of Intellectual Property Bureau Consumer Cooperatives 6. Patent application scope Photoionization mass spectrometer. 104. A device for measuring the end point of the removal of the target film covering the blocking film. One of the target film and the barrier film includes a nitride by a process that produces ammonia when in contact with nitride. The device includes a monitor that monitors the ammonia content when the target film is removed. 105. If a patent is applied The device according to item 104, wherein the process is chemical-mechanical polishing using a polishing slurry, and the ammonia is included in the polishing slurry, and the monitor further includes: a sampler for sampling ammonia in the slurry in a liquid form. 106 · If the device is in the scope of patent application No. 105, the sampler includes an ion selective electrode. 107 · If the device is in the scope of patent application No. 104, the process is for use Chemical-mechanical polishing of the polishing slurry, and the ammonia system is contained in the polishing slurry, which further includes an extractor for extracting chemical reaction products with gas from the slurry. 108. The device according to the scope of patent application No. 107, wherein the extractor Includes: an arrangement for bringing the first side of the hydrophobic film into contact with the slurry; an arrangement for bringing the second side of the hydrophobic film into contact with the gas stream; and an arrangement that allows chemical reaction products to pass through the film with the gas and become transported in the gas stream 109. The device according to item 108 of the patent application, wherein the extractor comprises a contactor, which contains microporous fibers. 110. The device according to item 107 of the patent application, wherein the monitor includes Fourier Paper Scale Gu + Guan Jia Standard (CNS) A4 specification (210 X 297 gong) (Please read the phonetic on the back? Matters before filling out this page}, -------- Order --------- 557356 A8 B8 C8 D8 6. Patent application Leaf conversion microwave spectrometer. 111. The device of patent application No. 107 in the patent application, in which the monitor includes a low-limit photoionization mass spectrometer. Device for concentrating substances, including: an extractor for extracting the existing substance by gas from a liquid, including an arrangement for contacting a first side of a hydrophobic permeable film with a liquid containing the substance; making a second of the film Each side is in contact with the airflow; and the device that allows the substance to pass through the membrane and become transported in the airflow; and a monitor that monitors the airflow to detect the substance. II3. Device such as patent application No. 112 , Where the concentration is less than or equal to 1.0 Mol. 5 Molar concentration. 114. The device of claim 112, wherein the extractor comprises a contactor which contains microporous fibers. 115. The device of claim 112, wherein the monitor comprises a Fourier transform microwave spectrometer. 116. The device of the scope of application for patent No. 112, wherein the monitor includes a low-limit photoionization mass spectrometer printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. II7 · —A method for detecting the removal end of the target film overlaid on the barrier film ', which is performed by chemical-mechanical polishing using a slurry, which includes the following steps: ⑻Using a polishing process that generates chemical reaction products in the slurry ， Remove the target film; 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557356 A8 B8 C8 D8 6. Scope of patent application. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. ⑼ Add a reagent that will produce characteristic results when reacting with chemical reaction products, and add it to the slurry; and ... (c) § When removing the target film , To monitor the characteristic results of the slurry. 118. A method as claimed in claim 117, wherein the characteristic result is a change in color. 119. The method of claim 117, wherein the characteristic result is light emission. 120. The method according to the scope of patent application No. 119, wherein the light emission is monitored by the photomultiplier method. 121. The method according to item 117 of the patent application, wherein the characteristic result is the formation of a precipitate. 122. The method of claim 121, wherein the formation of precipitates is monitored by light scattering. 123. The method of claim m of claim 1, further comprising the step of stopping polishing when the end point has been reached. 124. The method of claim 117, wherein the chemical reaction product is ammonia. 125. The method of claim 124 in which the reagent is a Nessler reagent and the characteristic result is a change in color. 126 · —A device for measuring the end point of the removal of the target film covering the barrier film 'is a chemical-mechanical polishing process that generates chemical reaction products in the slurry used in the polishing process. The device includes: A setting that adds a reagent that produces characteristic results when reacting with a chemical reaction product to the slurry; and -41-The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back first) Note: Please fill in this page for matters) Line 6. Scope of patent application A monitor that monitors the results of the slurry characteristics when the target film is removed. For example, the device of the patent application No. 126, wherein the adding dish setting includes a storage tank for holding a controlled amount of slurry from the polishing process; and a conveying system for adding the reagent to the storage tank. 128 =: The device of item 127 of the profit range ', where the conveying system is pulse 129. For the device of item 127 of the patent application, its steps include: emptying the storage tank and filling the storage tank with new slurry from the polishing process Settings. Say, for example: the device under the scope of patent 127, where the monitor is a color sensor. The device of patent application No. 127, wherein the monitor is a photomultiplier 132. For the device of scope No. 127 of the patent application, the monitor is an optical device. 133-A method for reducing the amount of gaseous products in a solution, which includes the following steps : (A) bringing the first side of the hydrophobic film into contact with the solution; ⑼ bringing the second side of the hydrophobic film into contact with an aqueous liquid stream; and (C) allowing the gaseous product to pass through the film as a gas and become water-containing It further includes the step of dissolving the solution and further including recycling the method liquid containing the 134 · method of patent application No. 133 through step 。. 135 · The method water of the scope of patent application No. 133 The liquid flow recirculates through step 136. The method of item 133 of the patent application scope, in which the solution is a polishing slurry -42- The scale of the scale is applicable to the Chinese National Standard (CNS) A4 specification (⑵〇 297 公 爱) 557356 A8 B8 C8 D8 6. The scope of patent application is the method of applying for the patent No. 135, where the gaseous product is gas. ⑽ The method of applying for the patent No. 136, including the aqueous liquid stream. HC1 〇139 ·-A device for reducing the amount of gaseous products in the falling liquid, comprising: a device for contacting a first side of a hydrophobic film with a solution; a device for contacting a second side of a 4 water-based film with an aqueous liquid stream And a device that allows the gaseous product to pass through the membrane as a gas and be transported in an aqueous liquid stream. 140. The device of claim 139, further comprising: a contactor containing microporous fibers; On the first side, the pump that pumps the solution through the contactor; and on the first side that cuts the dimension, the pump that pumps the aqueous liquid flow through the contactor. 141. Such as the scope of application for patent No. 139 A device further comprising a setting for recirculating the solution through the first contact setting. 142. A method of detecting an end point of removal of a target film overlaid on the barrier film, comprising the following steps: Ministry of Economic Affairs Intellectual Property Printed by the Bureau's Consumer Cooperative (a) using a process that selectively produces chemical reaction products with one of the barrier film and the target film to remove the target film; ⑼ Existing chemical reaction products are converted into individual products; ⑷ Generates stimulated gas molecules from the individual products; and (d) When the target film is removed, the content of light emitted from the stimulated gas molecules is monitored. Method of 142, in which the film is printed by dry etching of the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557356 A8 B8 C8 ----—_ D8-______ 6. The scope of application for patents is removed. Level 1 If the scope of patent application is No. 142 Method in which the film is removed by chemical polishing. ⑷. The method according to the scope of patent application, wherein the chemical reaction product is contained in the slurry which has been used for chemical mechanical polishing. 146. If the method according to item 145 of the patent application is applied, the step further includes a step of extracting the chemical reaction product with a gas from the polymer solution. 147. The method according to item 146 of the patent application, wherein the extraction step includes: contacting the first side of the hydrophobic film with the slurry; contacting the second side of the hydrophobic film with a gas stream; and allowing the chemical reaction product to The gas passes through the membrane and becomes carried in a gas stream. 148. The method of claim 147, wherein the conversion step is a catalyst conversion. 149. The method according to the scope of patent application No. 142, wherein the emitted light is monitored by the photomultiplier method. 150. The method according to item 142 of the patent application park, further comprising the step of stopping the removal process when the end point has been reached. 151. The method of claim 142, wherein the process is to selectively produce chemical reaction products with a barrier film. 152. The method of claim 151, wherein the content of the 'chemical reaction product increases when the target film is removed. 153. The method of claim 142, wherein the process is to selectively produce chemical reaction products with the target film. -44-This paper size is suitable for financial standards (CNS) A4 (210 X 297 public love) ------- .ϋ n ϋ ϋ ϋ ϋ one -0, II (Please read the precautions on the back first Write this page again thin) 丨 • Fill and fill in too much lineΦ- · 557356 A8 B8 C8 D8 Scope of patent application Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I54. If the method of applying for the scope of patent No. 153 is applied, the content of the chemical reaction product will be reduced when the target film is removed. 15 5-A method for removing the dots of a target film covering a barrier film, the target film and the barrier film-each containing a nitride including the following steps: During the process, the target film is produced, and the target film is removed; " The lice process (b) converts ammonia into individual products; and, when the target film is removed, the ammonia content is monitored. ⑼. The method according to the scope of application for patent No. 155, wherein nitrogen is produced individually. ^ Milk 157. Method of Patent Application No. 155. Mechanical polishing removal. 158. The method according to the scope of patent application No. 55, in the slurry. 159. The step of extracting ammonia by gas as in the method of patent application No. 1. 160. If the method of claim 159 of the scope of patent application, contact the first side of the hydrophobic film with the slurry; contact the second side of the hydrophobic film with the air stream; and allow ammonia to pass through the film with the gas and become in the air stream transport. 161. The method of claim 155, wherein the transformation step includes vector transformation. 162. Detecting the end point of the removal of the target film overlaid on the barrier film (please read the note on the back? Matters before filling out this page) where the film is by chemical _ where the ammonia is included in the polishing process- Including self-slurry, where the extraction steps include: ϋ 1 II line 0- · This paper rule S @ 家 standard (CNS) A4 specifications (21〗 x) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 557356 A8 B8 C8 _. ..______ D8 _____ VI. Patent application device 'It is a process that selectively produces chemical reaction products with one of the barrier film and the target film. The device includes: (a) the chemical reaction products are converted into individual products A converter; (b) an arrangement for generating excited molecules from the individual product; and (c) a monitor that monitors the amount of light emitted from the excited molecules when the target film is removed. 163. The device according to claim 162, wherein the converter includes a catalyst converter. 164. The device of claim 162, wherein the monitor includes a photomultiplier tube. 165. The device of claim 162, wherein the process is chemical-mechanical polishing using a polishing slurry, and the chemical reaction product is contained in the polishing slurry, which further includes extracting the chemical reaction product from the slurry with a gas. Extractor. 166. The device of the scope of application for patent No. 165, wherein the extractor comprises: a setting for bringing the first side of the hydrophobic film into contact with the slurry; a setting for bringing the second side of the hydrophobic film into contact with the gas stream; and allowing chemistry The reaction product passes through the membrane as a gas, and becomes a setting to be carried in a gas stream. 167. The device according to item 162 of the patent application scope further includes a setting for stopping the removal process when the end point has been reached. 168 · —A method for detecting the end point of removal of the target film covering the barrier film, including the following steps: Use a selective gaseous state with one of the barrier film and the target film " iimi--4β-This paper Standards are applicable to China National Tombs Standard (CNS) A4 specifications (210 X 29Γ) ----- -------------- installation -------- order ---- ----- (Please read the note on the back? Matters before filling out this page) 557356 A8 B8 C8 D8 VI. The process of applying for a patented chemical reaction product to remove the target film; when removing the target film, borrow low Limit the photoionization mass spectrum to monitor the content of the chemical reaction products. 169. For example, the method of patent application No. 168, in which the thin film is removed by dry etching. Im As the method of patent application No. 108, in which the thin film is by chemical A mechanical polishing is removed. 171. The method of claim 168, wherein the chemical reaction product is contained in a slurry that has been used in chemical mechanical polishing, and further includes a step of taking the chemical reaction product from the slurry in a gas year. 172 · If the scope of application for patent m The method wherein the extraction step includes: contacting the first side of the hydrophobic film with the slurry; contacting the second side of the hydrophobic film with a gas stream; and allowing the chemical reaction product to pass through the film with the gas and become transported in the gas stream 173 · If the method of applying for the scope of patent application No. 168, wherein the gaseous chemical reaction product is ammonia. # Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 174 · If the method of applying for the scope of patent application No. 168, it further includes when At the end point, the step of removing the process is stopped. 175. For example, the method in the scope of patent application No. 168, wherein the process and the trapping film selectively produce gaseous chemical reaction products. Tian 176. In the scope of patent application No. 168 Method, in which the amount of the gaseous chemical reaction product will increase when the target film is removed. 177. If the method of the scope of patent application No. 168, the process is related to the target -47- (Please read the note on the back? Matters? (Fill in this page again) Line Φ- · This paper ruler_Home Standard (& JNS) A4 Specification (210 X 297 mm 557356 A8 B8 C8 6. Scope of patent application Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The film selectively produces gaseous chemical reaction products. 178. The method of claim 168, wherein the amount of the gaseous chemical reaction product is reduced when the target film is removed. 179 · —A device for detecting the removal end of a target film covering a barrier film, which is a process for selectively generating a chemical reaction product with one of the target film and the barrier film. The device includes: When removing the target film, monitor the low limit photoionization mass spectrometer of the chemical reaction product content. 180. For the device in the scope of application for patent No. 179, wherein the process is chemical and mechanical polishing using a polishing slurry, and the reaction product is contained in the polishing slurry, which further includes extraction of the chemical reaction product from the slurry with gas. Device. 181. The device of claim 180, wherein the extractor comprises: a setting for bringing the first side of the hydrophobic film into contact with the slurry; a setting for bringing the second side of the hydrophobic film into contact with the air stream; and allowing chemistry The reaction product passes through the membrane as a gas, and becomes a setting to be carried in a gas stream. 182. The device of claim 181, wherein the extractor comprises a contactor which contains microporous fibers. -48- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) ----- Γ -------- installation ---- (Please read the note on the back first? (Please fill in this page for matters) Order ---------.