System and method for real-time measurement of particles in ozone

Abstract

A system and method for real-time measurement of particles in ozone is provided. The system includes an ozone reduction device that heats ozone from an ozone source along a spiral transport path to reduce it to oxygen gas, and a particle counter that measures particles in the oxygen gas in real time. The ozone source is optionally diverted to supply a portion of the ozone to the ozone reduction device and the remaining ozone to the process equipment. This allows the particle counter to measure particles in the oxygen gas in real time while the process equipment is performing a process. This prevents contamination with other non-ozone particles contained in the ozone, and certifies that the ozone gas supplied from the ozone generator as an ozone source, or the ozone tail gas discharged from the process equipment as an ozone source, does not contain contaminating particles.

Description

[Technical Field]

[0001] The present invention relates to a system and method for measuring particles contained in ozone gas, and in particular to a method that combines ozone gas reduction technology with particle measurement technology after the ozone has been reduced, and a system designed using this method. [Background technology]

[0002] Ozone has been found to be capable of oxidizing organic and / or metallic materials and is therefore applicable to the cleaning and processing of semiconductor wafers, for example to remove unwanted photoresist residues. Ozone can be used either in the gas phase (dry ozone technology) or dissolved in water to be used as ozone water (wet ozone technology). For example, ozone can be used to remove photoresist after a series of photolithography and etching processes. Dry ozone or wet ozone techniques can all be applied to the surface of a semiconductor wafer, and with dry ozone techniques, the surface of the semiconductor wafer is exposed to ozone gas and one or more gases to oxidize material at the surface of the wafer. According to wet ozone technology, the surface of a semiconductor wafer is exposed to ozone and a process fluid (eg, deionized (DI) water or a chemical solution) to oxidize material at the surface of the wafer.

[0003] The cleanliness of the wafer surface affects subsequent semiconductor processing and product yield; moreover, 50% of all production losses are caused by contamination of the wafer surface. The most common types of contamination are residues such as metals, organics and particles.

[0004] When ozone is used in the process of manufacturing semiconductor devices, contamination by impurities contained in the ozone, particularly contamination by metals, is a serious problem. Metals that are sources of contamination include, for example, metal electrodes in a reaction chamber that generates ozone through high-voltage discharge, or reaction products resulting from the reaction of ozone with a metal pipeline that supplies the ozone. These metal impurities have a significant effect on the function of semiconductor devices, affecting electrical properties such as conductivity, resistance, and dielectric constant. For example, metal contamination can cause leakage currents in pn structures, which in turn reduces the oxide breakdown voltage and shortens the carrier life cycle.

[0005] Conventional techniques use gas filters to remove impurities from the ozone used in the process of fabricating semiconductor devices. Conventional gas filters remove gas phase impurities, for example, by means of an adsorbent capable of adsorbing the impurities. Another conventional gas filter filters out impurities, which are solid particles, using a filtering material. Meanwhile, the prior art has been trying to reduce the metal impurities contained in the generated ozone by successively improving the electrode structure and electrode material that perform high voltage discharge in the ozone generator.

[0006] Ozone generators generate ozone by discharging electricity between metal electrodes, and metal particles generated at the metal electrodes are also a source of ozone contamination. To solve the above problems, the prior art (for example, Taiwan Patent Publication No. 200605208A) has proposed to install a molecular permeable membrane capable of filtering metal particles in an ozone gas supply system. Furthermore, prior art (e.g., U.S. Patent Nos. US9186647B2 and US9764268B2) has proposed attaching a gas filter to an ozone generator to filter out solid particles larger than 0.2 μm in diameter and remove impurities and foreign matter. However, it is difficult to determine whether the gas filters or molecular permeable membranes of these ozone generators retain their original filtering function after a certain period of use. Generally, inspection can only be performed by shutting down the equipment and scanning a wafer (empty slice) with an optical microscope.

[0007] In addition to cleaning, ozone can also create an oxide layer, which can act as a passivation layer and also as an interface layer. Ozone has extremely low stability and is easily decomposed into oxygen gas at room temperature. For this reason, ozone cannot be stored and is generally generated on-site by an ozone generator and used on-site. However, ozone is a gas that has adverse effects on the human body and the environment, and although it is naturally prone to decomposition into oxygen gas, this decomposition is slow, so that ozone tail gas cannot be discharged unless it is treated. And current technology does not provide a means to verify whether ozone tail gas emitted from an ozone source (eg, semiconductor processing equipment) contains contaminant particles. Currently, ozone can be decomposed into oxygen gas using ozone reduction technology. Ozone has a half-life of about 3 days at 20°C, but the half-life shortens as the temperature rises. According to the prior art, in order to completely reduce ozone to oxygen gas, extremely high temperatures (above about 420° C.) are required to achieve this effect. Furthermore, since conventional ozone reduction chambers are cylindrical, the time it takes for ozone gas to pass through such a cylindrical ozone reduction chamber is extremely short. Furthermore, with conventional ozone reduction technology, ozone comes into direct contact with the heating element, which is prone to corrosion.

[0008] To summarise, taking semiconductor processing as an example, the entire semiconductor process typically takes more than a month from wafer cutting to completion, meaning that any losses incurred would amount to hundreds of millions of dollars. Therefore, the key to all detection is to predict the loss and stop it immediately to prevent it from occurring. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Taiwan Patent Publication No. 200605208A [Patent Document 2] U.S. Patent No. 9186647B2 [Patent Document 3] U.S. Patent No. 9,764,268 B2 Summary of the Invention [Problem to be solved by the invention]

[0010] The main object of the present invention is to provide a system and method for instantly measuring particles in ozone, which combines the ozone reduction technology of an ozone reduction device with the particle (also called dust or fine particles) detection technology of a particle counter (also known as a particle size counter) to instantly measure the concentration of particle contamination in ozone gas, track the type of particle, and analyze the source of the contamination. [Means for solving the problem]

[0011] According to the present invention, a system for measuring particles in ozone in real time includes heating ozone from an ozone source along a spiral transport path to reduce it to oxygen gas; an ozone reduction device; a particle counter for real-time measurement of the number and / or size of particles in the oxygen gas; The present invention is characterized by comprising:

[0012] The system for real-time measurement of particles in ozone according to the present invention is characterized in that the ozone reduction device comprises an intake duct communicating with the ozone source, a gas transport pipe that introduces the ozone from the ozone source via the intake duct and transports the ozone along the spiral transport path, a heating element that supplies thermal energy to heat the ozone transported to the gas transport pipe, so that the ozone is heated by the thermal energy and reduced to oxygen gas as it flows along the spiral transport path, and an outlet duct that communicates with the gas transport pipe and discharges the oxygen gas obtained by reduction of the ozone.

[0013] The system for real-time measurement of particles in ozone according to the present invention is characterized in that the gas transport pipe is a spiral tube, and the outer circumferential surface of the heating element is fitted into the gas transport pipe.

[0014] The system for real-time measurement of particles in ozone according to the present invention is characterized in that the heating element directly heats only the ozone in the gas transport pipe, simultaneously heats the gas transport pipe and the ozone in the gas transport pipe, and / or indirectly heats the ozone in the gas transport pipe by heating the gas transport pipe.

[0015] The system for real-time measurement of particles in ozone according to the present invention further comprises an insulating member, which maintains the temperature of the ozone by covering one or more of the gas transport pipe, the heating element, the intake duct and / or the outlet duct.

[0016] The system for real-time measurement of particles in ozone according to the present invention further comprises a thermometer, which measures the temperature of the ozone in the gas transport pipe when heated by the thermal energy from the heating element.

[0017] The system for instantly measuring particles in ozone according to the present invention further comprises a temperature control element, which controls the thermal energy from the heating element based on the heating temperature measured by the thermometer, thereby heating the ozone to a predetermined temperature.

[0018] The system for real-time measurement of particles in ozone according to the present invention further comprises an intake end adapter and an outlet end adapter, the intake end adapter being connected to both the intake duct and the gas transport pipe so as to be positioned between them, and the outlet end adapter being connected to both the gas transport pipe and the outlet duct so as to be positioned between them.

[0019] The system for real-time measurement of particles in ozone according to the present invention further includes a cooling device, which cools the oxygen gas obtained when the ozone is heated and reduced in the ozone reduction device.

[0020] The system for real-time measurement of particles in ozone according to the present invention further comprises a process device, wherein the ozone source supplies at least a portion of the ozone to an ozone reduction device, whereby the at least a portion of the ozone is heated and reduced to the oxygen gas, and the ozone source supplies the remaining ozone to the process device, thereby performing a process step.

[0021] The system for real-time measurement of particles in ozone according to the present invention is characterized in that the particle counter real-timely measures the number and / or particle size of the particles in the oxygen gas obtained by heating and reducing at least a portion of the ozone when the process equipment performs the process step using the remaining ozone.

[0022] The system for real-time measurement of particles in ozone of the present invention is characterized in that the process equipment controls whether to continue or stop the introduction of the remaining ozone from the ozone source into the process equipment by determining whether the ozone is contaminated with the particles based on the number and / or particle size of the particles in the particle counter.

[0023] The system for real-time measurement of particles in ozone according to the present invention is characterized in that the ozone source divides and supplies at least a portion of the ozone and the remaining ozone using a dividing pipe, thereby supplying the at least a portion of the ozone to the ozone reduction device and the remaining ozone to the process device, respectively.

[0024] The system for real-time measurement of particles in ozone according to the present invention is characterized in that a control valve is provided between the ozone source and the diversion pipe, and the control valve controls the continuation or stop of the supply of at least a portion of the ozone and / or the remaining ozone depending on the quantity and / or particle size of the particles.

[0025] The system for real-time measurement of particles in ozone according to the present invention is characterized in that the particle counter determines the quantity and / or particle size of the particles by irradiating the oxygen gas with light from a light source, causing scattering or diffraction by the particles in the oxygen gas, and analyzing the characteristics of the light from the light source.

[0026] The system for real-time measurement of particles in ozone according to the present invention further comprises a pure oxygen gas source, which first supplies pure oxygen gas to the ozone reduction device until the number and / or particle size of the particles measured by the particle counter becomes zero before the ozone from the ozone source is heated and reduced to the oxygen gas in the ozone reduction device.

[0027] According to the method for real-time measurement of particles in ozone of the present invention, a system for real-time measurement of particles in ozone according to any one of claims 1 to 16 is provided, in which: an ozone supplying step using ozone from an ozone source; an oxidation-reduction step of heating and reducing ozone from an ozone source to oxygen gas by an ozone reduction device along a spiral transport path; a measuring step of instantly measuring the number and / or particle size of particles in the oxygen gas using a particle counter; The present invention is characterized by comprising:

[0028] The method for instantly measuring particles in ozone according to the present invention further includes a zero reset step after performing the ozone supply step and before performing the oxidation-reduction step, and is characterized in that the number and / or particle size of the particles measured by the particle counter becomes zero by the zero reset step.

[0029] The method for instantly measuring particles in ozone according to the present invention further includes a cooling step after the oxidation-reduction step and before the measurement step, and is characterized in that the cooling step cools the oxygen gas reduced by heating the ozone in the ozone reduction device.

[0030] The method for real-time measurement of particles in ozone according to the present invention is characterized in that it further includes a diversion step after the ozone supply step and before the oxidation-reduction step, and the diversion step allows the ozone to be supplied in a diverted manner. [Effects of the Invention]

[0031] The system and method for real-time measurement of particles in ozone according to the present invention has the following advantages. (1) It is possible to prevent the contamination of semiconductor wafers with other non-ozone particles contained in ozone, and to prove that ozone gas from an ozone source (e.g., an ozone generator) or ozone tail gas discharged from an ozone source (e.g., a semiconductor processing device) does not contain contaminating particles.

[0032] (2) The filtering effect of a gas filter placed at an ozone source (e.g., the gas inlet and gas outlet of an ozone generator) can be immediately grasped. For example, it can be immediately grasped whether the filtering effect of removing impurities and foreign matter is still maintained after a certain period of use.

[0033] (3) By combining the ozone reduction technology of the ozone reduction device with the particle detection technology of the particle counter, the size and quantity of particles contained in ozone gas can be measured in real time, thereby enabling the pollution concentration to be measured in real time and the type of particles to be tracked to analyze the pollution source.

[0034] (4) By using a spiral gas transport pipe (e.g., a spiral quartz pipe) as the ozone reduction chamber, the space occupied by the conventional cylindrical ozone reduction chamber is reduced and the heat transfer area is increased, ensuring that the ozone molecules flowing into the spiral gas transport pipe have sufficient time to be heated, and the ozone gas can be quickly reduced to oxygen gas. This makes it highly suitable for application to the reduction of large amounts of ozone gas.

[0035] (5) By fitting a spiral gas transport pipe around the outer surface of the heating element, the heating efficiency is better than that of conventional devices, and costs can be reduced. Problems such as corrosion of the heating element and damage to the particle counter caused by direct contact of ozone with the heating element and particle counter, which occur in conventional devices, can be avoided.

[0036] (6) The cooling device allows the oxygen gas to be cooled to an appropriate temperature before the oxygen gas, which is produced by heating and reducing ozone, enters the particle counter.

[0037] In order to better understand the technical features and achievable technical effects of the present invention, better embodiments and detailed descriptions are provided below. [Brief explanation of the drawings]

[0038] [Figure 1] 1 shows a first embodiment of a system for real-time measurement of particles in ozone according to the present invention; FIG. [Figure 2] 2A and 2B are diagrams showing the assembled state of the gas transport pipe and the heating element of the ozone reduction device shown in FIG. 1, where FIG. 2A shows the state before assembly and FIG. 2B shows the state after assembly. [Figure 3] FIG. 1 shows an ozone reduction experimental setup used in the system for real-time particle measurement in ozone according to the present invention. [Figure 4] FIG. 1 is a 10-second measurement diagram of an ozone reduction experiment using a system for real-time measurement of particles in ozone according to the present invention. [Figure 5] FIG. 1 is a 30-second measurement diagram of an ozone reduction experiment using a system for real-time particle measurement in ozone according to the present invention. [Figure 6] 1 shows a first embodiment of a method for real-time measurement of particles in ozone according to the present invention; FIG. [Figure 7] FIG. 2 shows a second embodiment of a system for real-time measurement of particles in ozone according to the present invention. [Figure 8] FIG. 2 shows a second embodiment of the method for real-time measurement of particles in ozone according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0039] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The proportions of the components in the drawings of the embodiments of the present invention are shown for ease of understanding and are not to scale. Furthermore, the dimensional ratios of the assemblies shown in the drawings are for the purpose of explaining the components and their structures, and the present invention is not limited to these. On the other hand, for ease of understanding, the same components in the following embodiments will be described with the same reference numerals.

[0040] Furthermore, terms used throughout the specification and claims generally have their ordinary meanings as used in this field, the subject matter disclosed herein, and in the particular context, unless otherwise specified. Some terms used to describe the present invention are explained below and elsewhere in the specification to provide those skilled in the art with additional guidance regarding the description of the present invention.

[0041] The use of "first," "second," "third," etc. in this article does not specifically indicate an order or sequence, nor is it used to limit the present invention. This is only used to distinguish between components or operations that are described with the same terminology.

[0042] Secondly, when this article uses terms such as "including," "comprising," "having," and "containing," they are all open terms, meaning including but not limited to.

[0043] The system and method for real-time particle measurement in ozone of the present invention combines the ozone reduction technology of an ozone reducer with the particle detection technology of a particle counter. In the ozone reduction technology, first, ozone from an ozone source is heated sufficiently to reduce it to oxygen gas while passing through a spiral transport path, and then the oxygen gas is introduced into a particle counter for particle detection.

[0044] Please refer to Figures 1 to 6. FIG. 1 shows a first embodiment of a system for real-time measurement of particles in ozone according to the present invention. FIG. 2 is a diagram showing the assembled state of the gas transport pipe and heating element of the ozone reduction device of the system for instantly measuring particles in ozone according to the present invention, where FIG. 2(I) shows the state before assembly, and FIG. 2(II) shows the state after assembly. FIG. 3 is a diagram showing an ozone reduction experimental setup used in the system for real-time measurement of particles in ozone according to the present invention. FIG. 4 is a 10-second measurement diagram of an ozone reduction experiment using the system for real-time particle measurement in ozone according to the present invention. FIG. 5 is a 30-second measurement diagram of an ozone reduction experiment using the system for real-time particle measurement in ozone according to the present invention. FIG. 6 shows a first embodiment of a method for real-time measurement of particles in ozone according to the present invention.

[0045] Please refer to Figures 1 to 6. A first embodiment of a system 1 for real-time measurement of particles in ozone according to the present invention comprises an ozone reduction device 300 and a particle counter 500 . The method for instantly measuring particles in ozone according to the present invention includes an ozone supply step S100 in which ozone 110 is supplied by an ozone source 100; an oxidation-reduction step S200 in which the ozone 110 supplied by the ozone source 100 in step S100 is heated and reduced to oxygen gas 120 by an ozone reduction device 300 along a spiral transport path P so that all of the ozone 110 transported along the spiral transport path P can be sufficiently heated and quickly reduced to oxygen gas 120; and a measurement step S400 in which a particle counter 500 is used to instantly measure the number and / or particle size of particles in the oxygen gas 120 obtained by heating and reducing the ozone 110 in the ozone reduction device 300. According to the present invention, all of the ozone 110 entering the ozone reduction device 300 can be quickly and sufficiently heated and reduced to oxygen gas 120, and the concentration of particle contamination contained in the ozone 110 from the ozone source 100 can be measured immediately, so that the type of particle can be tracked and the source of the contamination can be analyzed. For example, after a gas filter disposed in the ozone source 100 (e.g., the gas inlet and gas outlet of an ozone generator) has been used for a certain period of time, it can be immediately known whether it still has the effect of filtering out impurities and foreign substances, thereby preventing contamination of semiconductor wafers by other non-ozone particles contained in the ozone 110 and proving that the ozone gas from the ozone source 100 (e.g., an ozone generator) or the ozone tail gas discharged from the ozone source 100 (e.g., a semiconductor processing device) does not contain contaminating particles.

[0046] The ozone reduction device 300 of the system 1 for real-time particle measurement in ozone according to the present invention is for reducing ozone 110 from the ozone source 100 to oxygen gas 120 . The ozone reduction device 300 according to the present invention includes an intake duct 10 , a gas transport pipe 20 , a heating element 30 , and an outlet duct 12 . Both ends of the gas transport pipe 20 communicate with the intake duct 10 and the outlet duct 12, respectively. The intake duct 10 is in communication with the ozone source 100 and is for introducing ozone 110 from the ozone source 100 . The type or application of the ozone source 100 according to the present invention is not limited. For example, since the ozone 110 from the ozone source 100 can be used in a semiconductor process such as cleaning the surface of a semiconductor wafer, the amount of ozone 110 introduced into the intake duct 10 may be, for example, only a portion of the ozone production amount (also referred to as the ozone supply amount) of the ozone source 100, and may further be, for example, excess ozone 110 (i.e., not affecting the performance of the semiconductor process) or ozone 110 supplied in accordance with measurement needs. Of course, the present invention is not limited to these.

[0047] The gas transport pipe 20 of the ozone reduction device 300 introduces ozone 110 from the ozone source 100 via the intake duct 10 . One of the features of the present invention is that the gas transport pipe 20 is a transport path P having a spiral shape, and the ozone 110 is transported along the spiral transport path P. The heating element 30 generates thermal energy to heat the ozone 110 being transported to the gas transport pipe 20, and as the ozone 110 flows along the spiral transport path P, it is heated by the thermal energy from the heating element 30 and reduced to oxygen gas 120. In other words, in the present invention, the gas transport pipe 20 having a hollow spiral structure is used as an ozone reduction chamber, and the ozone 110 not only flows along the spiral transport path P inside the gas transport pipe 20, but also performs the oxidation-reduction step S200, and the ozone 110 can be prevented from coming into contact with the heating element 30. The gas transport pipe 20 is, for example, a hollow spiral pipe, and is made of a spiral quartz pipe. The gas transport pipe 20 is attached to the heating element 30 so as to have a spiral shape, and is fitted onto the outer circumferential surface of the heating element 30, for example. As a result, the heating element 30 is located within the spiral of the spiral gas transport pipe 20 . The gas transport pipe 20 according to the present invention includes, for example, a hollow spiral pipe or is configured as a hollow spiral pipe, thus forming the spiral transport path P described above.

[0048] The heating element 30 of the present invention is an electric heater, such as a ceramic heating tube, but is not limited thereto. The heating element 30 may be any conventional heater, such as a resistance heater or a heat exchange heater. In the present invention, a spiral quartz tube is used to transport ozone gas. This increases the contact area (i.e., heat transfer area) between the ozone 110 and the back wall of the spiral quartz tube, and ensures that the ozone 110 gas molecules flowing into the spiral quartz tube have sufficient time to be heated, so that the ozone 110 is sufficiently reduced to oxygen gas 120 while flowing along the spiral transport path, i.e., before the ozone 110 is discharged from the spiral quartz tube. According to the present invention, ozone 110 can be rapidly reduced to oxygen gas 120, so it is very suitable for application to the reduction of a large amount of ozone gas. On the other hand, in the present invention, the method of heating the ozone 110 is not particularly limited, and the heating element 30 of the present invention optionally directly heats only the ozone 110, simultaneously heats the gas transport pipe 20 and the ozone 110 in the gas transport pipe 20, and / or indirectly heats the ozone 110 in the gas transport pipe 20 by heating the gas transport pipe 20. This is determined by the material of the gas transport pipe 20 and the heating type of the heating element 30 .

[0049] The outlet duct 12 of the ozone reduction device 300 according to the present invention communicates with the gas transport pipe 20 . As a result, the oxygen gas 120 obtained by reducing the ozone 110 can be discharged. The shape of the outlet duct 12 according to the present invention is not particularly limited, and may be a straight pipe, a curved pipe, a spiral pipe, a combination thereof, or any other shape.

[0050] On the other hand, the ozone reduction device 300 according to the present invention further includes a heat insulating member 50 as an option. The insulating member 50 can ensure uniform heating temperature and prevent rapid temperature drop, so the insulating member 50 may selectively cover any suitable position or member, for example, one or more of the gas transport pipe 20, the heating element 30, the intake duct 10 and / or the outlet duct 12. This makes it possible to maintain the temperature achieved by heating the ozone 110, and for example, the inside of the gas transport pipe 20 can be maintained at a predetermined temperature. This predetermined temperature is, for example, a temperature at which ozone 110 is reduced to oxygen gas 120 . The heat insulating member 50 according to the present invention employs, for example, ceramic fiber, but the present invention is not limited to this. The dimensions and specifications of the heat insulating member 50 are not particularly limited, and any heat insulating member that can achieve the effect of heat insulation and heat retention falls within the scope of protection claimed by the present invention. The predetermined temperature is, for example, 350° C., but the present invention is not limited thereto. Since the half-life of the ozone 110 is inversely proportional to the temperature, the predetermined temperature is set according to, for example, the length of the spiral transport path P and / or the flow rate of the ozone 110. For example, if the length of the spiral transport path P is approximately 276 cm, the inner diameter of the gas transport pipe 20 is approximately 4 mm, and the diameter of the spiral structure is approximately 50 mm, when the flow rate of ozone 110 is approximately 27 L / min, the residence time of ozone 110 in the gas transport pipe 20 is approximately 77 mS. In other words, the ozone 110 is fully reduced to the oxygen gas 120 before being discharged from the ozone reduction device 300 according to the present invention, or a predetermined proportion of the ozone 110 is reduced to the oxygen gas 120 . Any gas delivery pipe 20 specifications and corresponding intended temperatures are within the scope of the claimed protection of the present invention. The above-mentioned predetermined proportions are determined according to actual needs and are not particularly limited. The calculation of the time that the ozone 110 stays in the gas transport pipe 20 employs a conventional equation for the relationship between speed, distance, and time, and therefore the explanation is omitted.

[0051] The ozone reduction device 300 according to the present invention further optionally includes a thermometer 60 and / or a temperature control member 70. The thermometer 60 is for measuring the temperature of the ozone 110 in the gas transport pipe 20 when the ozone 110 is heated by the thermal energy from the heating element 30 . The temperature control member 70 controls the thermal energy from the heating element 30 to heat the ozone 110 . To explain this as an example, the temperature control member 70 is electrically connected to the thermometer 60 and the heating element 30, and controls the thermal energy from the heating element 30 based on the temperature measured by the thermometer 60, thereby heating the ozone 110 to the above-mentioned predetermined temperature. The thermometer 60 is installed, for example, above the middle section of the gas transport pipe 20 and measures the temperature. The temperature control member 70 is located, for example, outside the heat insulating member 50 and controls the temperature to which the ozone 110 is heated. The thermometer 60 and temperature control member 70 of the present invention may employ, for example, conventional temperature sensors and temperature controllers.

[0052] The ozone reduction device 300 according to the present invention further optionally includes an intake end adapter 40 and an outlet end adapter 42 . The intake end adapter 40 is located between the intake duct 10 and the gas transport pipe 20 and connects to both, and the outlet end adapter 42 is located between the gas transport pipe 20 and the outlet duct 12 and connects to both. The intake end adapter 40 and / or the outlet end adapter 42 employ a structure in which, for example, Teflon (registered trademark) covers stainless steel, but the present invention is not limited to this, and for example, a stainless steel layer may be covered on the outer surface of the Teflon layer.

[0053] The system 1 for real-time measurement of particles in ozone according to the present invention further optionally comprises a cooling device 400 . The method for real-time measurement of particles in ozone according to the present invention further includes an optional cooling step S300 after performing the oxidation-reduction step S200 and before performing the measurement step S400. In the cooling step S300, the cooling device 400 cools the oxygen gas 120 obtained by heating and reducing the ozone 110 in the ozone reduction device 300. For example, the temperature of the oxygen gas 120 discharged from the gas transport pipe 20 is lowered. The cooling device 400 is provided, for example, in the outlet duct 12 or between the gas transport pipe 20 and the outlet duct 12 . The cooling device 400 may be installed in any position as long as it can achieve the cooling effect, and all of these are within the scope of protection claimed by the present invention. The cooling device 400 may be, for example, an air-cooled, liquid-cooled, phase-change, or hybrid cooling device, but the present invention is not limited to these. As long as the temperature of the oxygen gas 120 can be reduced, any type of cooling device 400 falls within the scope of protection claimed by the present invention. On the other hand, in the present invention, the oxygen gas 120 obtained by heating and reducing the ozone 110 in the ozone reduction device 300 by, for example, an exhaust member (e.g., an exhaust pump) (not shown) can be selectively sucked into the cooling device 400 to obtain the cooling effect. The location where the exhaust member is installed is not particularly limited, and may be installed, for example, at any position in the outlet duct 12. As long as the oxygen gas 120 can be cooled by the cooling device 400, all of these fall within the scope of protection claimed by the present invention.

[0054] The system 1 for real-time measurement of particles in ozone according to the present invention uses a particle counter 500 to real-time measure the number and / or particle size of particles in cooled oxygen gas 120, for example, to real-time measure the particle contamination concentration contained in ozone 110 from an ozone source 100, and to analyze the source of contamination by tracking the type of particles. The particle counter 500 according to the present invention is not particularly limited in type or operating principle, and any particle counter that can measure particles falls within the scope of protection claimed by the present invention. For example, a commercially available particle counter 500 or any other technique for detecting particles or particle size may be employed, and therefore the description thereof is omitted. For example, the particle counter 500 is provided with a light source (for example, a collimated light source) that irradiates the oxygen gas 120 with light, causing particles suspended in the oxygen gas 120 to scatter or diffract. The characteristics of the light source are then analyzed to analyze the size and number of the suspended particles. More specifically, the particle counter 500 is a device that measures the size and concentration of particles in ozone, and its principle is to infer the size and concentration of particles by detecting the scattering and absorption of light by particles. When using particle counter 500, for example, oxygen gas 120 passes through small holes or passages and the size and number of particles is measured by optical detection. The type or concentration of particles that can be measured by particle counter 500 is not particularly limited.

[0055] The method for real-time particle measurement in ozone according to the present invention further includes an optional zero reset step S500 after performing the ozone supply step S100 and before performing the progressive oxidation-reduction step S200. By the zero reset step S500, the result measured by the particle counter 500 becomes zero. The system 1 for real-time particle in ozone measurement according to the present invention optionally includes a pure oxygen gas source 600 . During the zero reset step S500, the pure oxygen gas source 600 supplies pure oxygen gas 200 to the ozone reduction device 300 until the value (e.g., the number and / or particle size of particles) measured by the particle counter 500 becomes zero, and the ozone reduction device 300 heats and reduces the ozone 110 from the ozone source 100 to oxygen gas 120. To explain this by way of example, in the present invention, for example, the temperature control member 70 is turned on, the spiral gas transport pipe 20 is preheated to a high temperature (for example, the thermometer 60 is set to about 550°C), the pure oxygen gas source 600 (for example, a high-pressure liquid-phase oxygen gas cylinder) is opened, and the pure oxygen gas 200 is supplied to the ozone source 100 (for example, an ozone generator), and the flow rate of the pure oxygen gas 200 is controlled to about 2.83 L / min by the mass flow controller 82. Before introducing ozone 110 into intake duct 10, pure oxygen gas 200 is first introduced, and pure oxygen gas 200 is continuously introduced into intake duct 10 until the 0.1 μm value (e.g., particle number and / or particle size) of particle counter 500 becomes zero. When the particle counter 500 reaches zero, the intake duct 10 is free of particle contamination. Next, the ozone source 100 (eg, an ozone generator) is turned on to generate ozone 110 which flows into the intake duct 10 . The pressure controller 86 controls the back pressure to be about 30 PSi, and the ozone concentration sensor 84 measures the ozone 110 concentration to be about 230 g / Nm 3 When this occurs, ozone 110 is introduced into the ozone reduction device 300, and the oxidation-reduction step S200 is carried out. As the ozone 110 passes through the spiral gas delivery pipe 20 at a temperature of about 550° C., it is heated and reduced to oxygen gas 120 . The reduced oxygen gas 120 flows into, for example, a cooling device 400 and is cooled. Next, the cooled oxygen gas 120 flows again into the particle counter 500 to measure the particles. The particle size measurement range includes, for example, about 0.1 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.7 μm, and 1.0 μm. Each test is performed for about 60 seconds, and each test is performed for about 360 seconds. For example, the test is performed twice.

[0056] As shown in Table 1, the measurement results of the particle counter 500 showed that eight particles were measured in the first experiment and six particles were measured in the second experiment. There are 3 to 4 particles with a particle size of 0.2 μm or less and 0.2 μm. As can be seen from the experimental results in Table 1, by combining ozone reduction technology with particle measurement technology, the present invention allows for measurement of particles in ozone 110. This prevents other non-ozone particles contained in the ozone 110 from contaminating the target object (for example, the surface of the semiconductor wafer 800).

[0057] Table 1: Particle measurement results. JPEG0007815494000002.jpg52145

[0058] Please refer to Figures 3 to 5. FIG. 3 is a diagram showing an ozone reduction experimental setup according to the present invention. FIG. 4 is a 10-second measurement diagram of an ozone reduction experiment according to the present invention. FIG. 5 is a 30-second measurement diagram of an ozone reduction experiment according to the present invention. In the present invention, the ozone concentration sensor 84 measures the ozone concentration on both sides of the gas transport pipe 20 (for example, measurement point A and measurement point B), and the result of ozone reduction by the ozone reduction device 300 of the present invention can be known. For example, in the present invention, the ozone source 100 is an ozone generator, and in the present invention, a pure oxygen gas source 600 (e.g., a high-pressure liquid-phase oxygen gas cylinder) supplies pure oxygen gas 200 to the ozone source (e.g., an ozone generator), whereby the pure oxygen gas 200 is reacted to become ozone gas, and ozone 110 is supplied. In the present invention, before introducing ozone 110 into the gas transport pipe 20 of the ozone reduction device 300, the gas transport pipe 20 is heated to a high temperature by the temperature control member 70, and the thermometer 60 indicates, for example, about 350°C. Thereafter, the ozone 110 flows into the gas transport pipe 20 of the ozone reduction device 300 via the intake duct 10. In more detail, ozone 110 flows into the gas transport pipe 20 via the intake end adapter 40, and the temperature of the gas transport pipe 20 is about 350°C. After passing through the gas transport pipe 20 at 350°C, the ozone 110 enters the outlet duct 12 via the outlet end adapter 42. The reduced gas passes through the cooling device 400, where the ozone concentration is measured again by the ozone concentration sensor 84 (at measurement point B), and then is discharged. In the present invention, for example, the mass flow controller 82 controls the flow rate of the oxygen gas 200 to 27 L / min, and the pressure controller 86 controls the back pressure to 30 PSi. The ozone reduction device 300 according to the present invention is installed on, for example, a workbench 310, and an ozone reduction experiment is carried out, but the present invention is not limited to this.

[0059] Referring to Figure 4, it can be seen from the data shown in Figure 4 that when the ozone concentration at measurement point A rapidly increases from 0.02 wt% to 0.14 wt%, the ozone reduction device 300 according to the present invention can reduce 0.14 wt% ozone to 0.01 wt% (measurement point B) in less than one second.

[0060] Please refer to Fig. 5. Fig. 5 shows data for 30 minutes obtained by measuring the ozone concentration (measurement point A, measurement point B) while continuously carrying out the ozone reduction reaction using the ozone reduction device 300 according to the present invention. As can be seen from FIG. 5, even after long-term operation, the ozone reduction device 300 according to the present invention still has a good response.

[0061] In the above ozone reduction experiment, the flow rate of ozone 110 from the ozone source 100 was approximately 27 L / min, and the ozone concentration was approximately 15.3 wt% (measurement point A). This translates to approximately 354 g / hr of ozone being generated, which is more than three times the concentration of ozone typically used for sterilizing spaces. In the present invention, the gas transport pipe 20 (for example, a spiral quartz pipe) allows sufficient time for the ozone 110 to be heated and quickly reduced to oxygen gas 120 (although the ozone 110 is barely detectable at measurement point B). In addition, in the present invention, the heat insulating member 50 (for example, a heat insulating material layer) is used, so that ozone reduction can be carried out stably for a long period of time.

[0062] Please refer to Figures 7 and 8. And please refer to Figures 1 to 6. FIG. 7 shows a second embodiment of a system for real-time measurement of particles in ozone according to the present invention. FIG. 8 shows a second embodiment of the method for real-time measurement of particles in ozone according to the present invention. The second embodiment differs from the first embodiment in that a process device 700 is further added to the system 1 for real-time measurement of particles in ozone. The process device 700 performs the process step S700 and further includes a flow dividing pipe 105. The diversion pipe 105 performs the diversion step S600. For example, when the ozone source 100 supplies ozone 110, at least a portion 110a of the ozone 110 diverted from the ozone source 100 is supplied to the ozone reduction device 300 by the diversion pipe 105. As a result, at least a portion 110a of the ozone 110 is heated and reduced to oxygen gas. The remaining ozone 110 b diverted from the ozone source 100 is supplied to the process device 700 . This causes the process to proceed to step S700. The process tool 700 and process step S700 described above are not limited to the semiconductor manufacturing field, but can also be applied to any field where particles in ozone gas are to be measured.

[0063] In the present invention, for example, the process step S700 is performed by the process equipment 700, and the measurement step S400 is also performed. This allows the number and / or size of particles in the ozone 110 to be measured. The ozone source 100 performs a flow dividing step (S600) using, for example, a flow dividing pipe 105 (for example, a three-way pipe). As a result, the ozone 110 is divided and supplied to the ozone reduction device 300 and the process device 700. For example, at least a portion 110a of the ozone 110 is supplied to the ozone reduction device 300, and the remaining portion 110b of the ozone 110 is supplied to the process device 700. This allows the particle counter 500 to instantly measure the number and / or particle size of particles in the oxygen gas 120 reduced by heating at least a portion 110a of the ozone 110 while the process device 700 performs a process using the remaining 110b of the ozone 110. The process tool 700 can determine whether the ozone 110 is contaminated with particles, for example, by selectively counting the number and / or size of particles detected by the particle counter 500 . This controls whether to continue or stop the introduction of the remaining ozone 110 110 b from the ozone source 100 into the process device 700 . For example, a control valve 107 is optionally provided between the ozone source 100 and the shunt 105 . This allows for controlling whether the supply of ozone 110 to at least part 110a and / or the remaining part 110b is continued or stopped depending on, for example, the number and / or size of the particles.

[0064] More specifically, if the process tool 700 is a semiconductor photoresist removal tool, the semiconductor photoresist removal tool includes a reaction chamber 710 and a stage 720 on which a wafer 800 (also called a target) can be placed. A nozzle 740 is provided at an opening 730 above the reaction chamber 710, and the nozzle 740 is connected to an ozone source 100 (e.g., an ozone generator) via piping 750 to supply ozone 110 to a wafer 800 (e.g., a semiconductor wafer) in the reaction chamber 710.

[0065] A pipe 750 connecting the ozone source 100 (for example, an ozone generator) and the nozzle 740 is provided with, for example, a control valve 107 and a branch pipe 105 . The ozone 110 is divided by the dividing pipe 105 and supplied to the ozone reduction device 300 via the intake duct 10 , and then supplied to the process device 700 via the piping 750 .

[0066] The ozone reduction device 300 according to the present invention reduces ozone 110 to oxygen gas 120 using, for example, a gas transport pipe 20 (e.g., a spiral quartz tube) and a heating element 30 (e.g., a ceramic heater), and then the oxygen gas 120 is cooled in a cooling device 400 and flows into a particle counter 500. When particle counter 500 detects particles, process equipment 700 (eg, semiconductor photoresist removal equipment) quickly takes appropriate measures, such as closing control valve 107 to stop the supply of ozone 110. As a result, the present invention has the effect of preventing the occurrence of loss or immediately stopping the occurrence of loss. Although the present invention has been described using an example in which it is applied to the semiconductor manufacturing field, the present invention is not limited to the semiconductor manufacturing field and can be effectively applied to any field in which it is desired to measure particles in ozone gas.

[0067] The system and method for real-time measurement of particles in ozone according to the present invention has the following advantages. (1) It is possible to prevent the contamination of semiconductor wafers with other non-ozone particles contained in ozone, and to prove that ozone gas from an ozone source (e.g., an ozone generator) or ozone tail gas discharged from an ozone source (e.g., a semiconductor processing device) does not contain contaminating particles.

[0068] (2) The filtering effect of a gas filter placed at an ozone source (e.g., the gas inlet and gas outlet of an ozone generator) can be immediately grasped. For example, it can be immediately grasped whether the filtering effect of removing impurities and foreign matter is still maintained after a certain period of use.

[0069] (3) By combining the ozone reduction technology of the ozone reduction device with the particle detection technology of the particle counter, the size and quantity of particles contained in ozone gas can be measured in real time, thereby enabling the pollution concentration to be measured in real time and the type of particles to be tracked to analyze the pollution source.

[0070] (4) By using a spiral gas transport pipe (e.g., a spiral quartz pipe) as the ozone reduction chamber, the space occupied by the conventional cylindrical ozone reduction chamber is reduced and the heat transfer area is increased, ensuring that the ozone molecules flowing into the spiral gas transport pipe have sufficient time to be heated, and the ozone gas can be quickly reduced to oxygen gas. This makes it highly suitable for application to the reduction of large amounts of ozone gas.

[0071] (5) By fitting a spiral gas transport pipe around the outer surface of the heating element, the heating efficiency is better than that of conventional devices, and costs can be reduced. Problems such as corrosion of the heating element and damage to the particle counter caused by direct contact of ozone with the heating element and particle counter, which occur in conventional devices, can be avoided.

[0072] (6) The cooling device allows the oxygen gas to be cooled to an appropriate temperature before the oxygen gas, which is produced by heating and reducing ozone, enters the particle counter.

[0073] The above description is by way of example only and is not limiting. Any equivalent modifications or variations thereto that do not depart from the spirit and scope of the present invention are included within the scope of the claims. [Explanation of symbols]

[0074] 1. A system for real-time measurement of particles in ozone 10 intake duct 12 Exit duct 20 Gas Transmission Pipe 30 Heating element 40 Intake end adapter 42 Outlet end adapter 50 Heat insulating materials 60 thermometer 70 Temperature control materials 82 Mass flow controller 84 Ozone concentration sensor 86 Pressure Controller 100 Ozone Source 105 Diversion tube 107 Control valve 110 Ozone 110a Some ozone 110b Remaining ozone 120 Oxygen gas 200 pure oxygen gas 300 Ozone reduction device 310 Workbench 400 Cooling device 500 particle counter 600 Pure oxygen gas source 700 Process Equipment 710 Reaction Chamber 720 Stage 730 Opening 740 nozzle 750 Piping 800 wafers P spiral transport route A, B measurement points S100 Ozone Supply Step S200 Redox step S300 Cooling Step S400 Measurement Step S500 Zero Reset Step S600 Diversion Step S700 Process execution steps

Claims

1. an ozone reduction device that heats and reduces ozone from an ozone source to oxygen gas along the spiral transport path; a particle counter for instantly measuring the number and / or size of particles in the oxygen gas; 1. A system for real-time measurement of particles in ozone, comprising:

2. The ozone reduction device is an intake duct in communication with the ozone source; a gas transport pipe that introduces the ozone from the ozone source via the intake duct and transports the ozone along the spiral transport path; a heating element that supplies thermal energy to heat the ozone transported through the gas transport pipe, so that the ozone is heated by the thermal energy and reduced to the oxygen gas while flowing along the spiral transport path; an outlet duct communicating with the gas transport pipe and discharging the oxygen gas obtained by reducing the ozone; 2. The system for real-time measurement of particles in ozone according to claim 1, comprising:

3. 3. The system for real-time measurement of particles in ozone according to claim 2, wherein the gas transport pipe is a spiral tube and is fitted onto the outer periphery of the heating element.

4. 3. The system for real-time measurement of particles in ozone described in claim 2, characterized in that the heating element directly heats only the ozone in the gas transport pipe, simultaneously heats the gas transport pipe and the ozone in the gas transport pipe, and / or indirectly heats the ozone in the gas transport pipe by heating the gas transport pipe.

5. 3. The system for real-time measurement of particles in ozone as described in claim 2, further comprising an insulating member that maintains the temperature of the ozone by covering one or more of the gas transport pipe, the heating element, the intake duct, and / or the outlet duct.

6. The system for real-time measurement of particles in ozone described in claim 2, further comprising a thermometer, which measures the temperature of the ozone in the gas transport pipe heated by the thermal energy from the heating element.

7. The system for instantly measuring particles in ozone as described in claim 6, further comprising a temperature control element, wherein the temperature control element controls the thermal energy from the heating element based on the heating temperature measured by the thermometer to heat the ozone to a predetermined temperature.

8. 3. The system for real-time measurement of particles in ozone as described in claim 2, further comprising an intake end adapter and an outlet end adapter, wherein the intake end adapter is connected to both the intake duct and the gas transport pipe so as to be positioned between them, and the outlet end adapter is connected to both the gas transport pipe and the outlet duct so as to be positioned between them.

9. 2. The system for real-time measurement of particles in ozone according to claim 1, further comprising a cooling device, which cools the oxygen gas obtained when the ozone is heated and reduced in the ozone reduction device.

10. 2. The system for real-time measurement of particles in ozone of claim 1, further comprising a process device, wherein the ozone source performs a process step by supplying at least a portion of the ozone to an ozone reduction device, where the at least a portion of the ozone is heated and reduced to the oxygen gas, and the ozone source performs a process step by supplying the remaining ozone to the process device.

11. 11. The system for real-time measurement of particles in ozone described in claim 10, characterized in that the particle counter real-timely measures the number and / or particle size of the particles in the oxygen gas obtained by heating and reducing at least a portion of the ozone when the process equipment performs the process step using the remaining ozone.

12. 12. The system for instantly measuring particles in ozone as described in claim 11, characterized in that the process equipment controls whether to continue or stop the introduction of the remaining ozone from the ozone source into the process equipment by determining whether the ozone has been contaminated with the particles based on the number and / or particle size of the particles in the particle counter.

13. 11. The system for real-time measurement of particles in ozone described in claim 10, characterized in that the ozone source supplies the at least a portion of the ozone and the remaining ozone by dividing the ozone and the remaining ozone through a dividing pipe, thereby supplying the at least a portion of the ozone to the ozone reduction device and the remaining ozone to the process device, respectively.

14. 14. The system for real-time measurement of particles in ozone described in claim 13, characterized in that a control valve is provided between the ozone source and the diversion pipe, and the control valve controls the continuation or stopping of the supply of at least a portion of the ozone and / or the remaining ozone depending on the quantity and / or the particle size of the particles.

15. The particle counter is characterized in that it irradiates the oxygen gas with light from a light source, causing scattering or diffraction by the particles in the oxygen gas, and determines the quantity and / or particle size of the particles by analyzing the characteristics of the light from the light source.

16. 2. The system for real-time measurement of particles in ozone described in claim 1, further comprising a pure oxygen gas source, wherein the pure oxygen gas source first supplies pure oxygen gas to the ozone reduction device until the number and / or the particle size of the particles measured by the particle counter becomes zero before the ozone from the ozone source is heated and reduced to the oxygen gas in the ozone reduction device.

17. 17. A method for measuring particles in ozone in real time by a system for measuring particles in ozone in real time according to any one of claims 1 to 16, comprising: an ozone supply step of supplying the ozone from the ozone source; an oxidation-reduction step of heating and reducing the ozone from the ozone source to the oxygen gas by the ozone reduction device along the spiral transport path; a measuring step of instantly measuring the number and / or the particle size of the particles in the oxygen gas by the particle counter; 1. A method for real-time measurement of particles in ozone, comprising:

18. 18. The method for instantly measuring particles in ozone described in claim 17, further comprising a zero reset step after performing the ozone supply step and before performing the oxidation-reduction step, wherein the zero reset step causes the number and / or particle size of the particles measured by the particle counter to become zero.

19. 18. The method for real-time measurement of particles in ozone described in claim 17, further comprising a cooling step after performing the oxidation-reduction step and before performing the measurement step, wherein the cooling step cools the oxygen gas reduced by heating the ozone in the ozone reduction device.

20. 18. The method for real-time measurement of particles in ozone described in claim 17, further comprising a dividing step after performing the ozone supply step and before performing the oxidation-reduction step, wherein the dividing step allows the ozone to be divided and supplied.

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