JP5303140B2 - Substrate processing process exhaust purification method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for continuously and stably circulating and supplying cleaned and temperature/humidity-controlled air to a clean work space over a long period of time by cleaning the exhaust air containing molecular contaminants exhausted from the clean work space in a substrate treatment process, in manufacturing LCDs, or the like, using an adsorbing material, after performing temperature/humidity control first without stopping the operation of a manufacturing equipment line. <P>SOLUTION: A method for cleaning exhausted air in a substrate treatment process cleans and controls the temperature and humidity of the exhaust air, in a substrate treatment process in manufacturing LCDs to circulate and supply it. The exhaust air is taken into a humidifying/cooling/heating apparatus as process air, to obtain humidified/cooled/heated air; and this is passed through a batch-type temperature swing adsorbing device by using the air taken in from the indoors or the outdoors as regenerated air, and temperature/humidity control and removal of molecular contaminants and particulate contaminants are carried out. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to ammonia, silane coupling agent, silanol discharged from a glass substrate processing step in manufacturing a liquid crystal display (hereinafter referred to as LCD) or a color filter of a color liquid crystal display, or a silicon substrate processing step in semiconductor manufacturing. Cleaning, temperature control and humidity control to remove molecular pollutants and particulate pollutants in the processing air by taking in exhaust containing alkenyl, silylating agent, siloxane, resist ink solvent, etc. The present invention relates to a method that enables continuous and stable circulation supply to a clean work space installed during the substrate processing step without interrupting work in the clean work space.

  A substrate processing step in LCD manufacturing or semiconductor manufacturing is a step of applying, exposing, developing or baking resist ink. In that processing step, a silane coupling agent is usually primed prior to applying a resist ink to a glass substrate or silicon substrate. Particularly in LCD manufacturing in recent years, it is necessary to further improve the yield in the circuit formation process with the increase in size of the glass substrate, so that hexamethyl dimethyl which exhibits the ability to further enhance the adhesion between the glass substrate and the resist film. Silazane (hereinafter referred to as HMDS) is frequently used.

  When HMDS is applied on a glass substrate and then resist ink is applied and baked, HMDS, ammonia and trimethylsilanol (hereinafter referred to as TMS), which are decomposition products of HMDS, and resist ink are applied according to the chemical formula shown in the following formula (1). Solvents and the like become molecular contaminants and scatter into the clean work space around the glass substrate. At this time, as shown by the equation (1), the number of molecules of TMS scattered is twice that of ammonia scattered.

(Oxide film of substrate) -OH + (1/2) (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ + (resist) -OH → (substrate oxide film) -O- (resist) + (1/2) NH ₃ + (CH ₃ ) ₃ SiOH
(1)

  Even when a silane coupling agent other than HMDS is used, the silane coupling agent, its decomposition products, silanols, siloxanes, silylating agents, resist ink solvents, etc. become molecular pollutants and become glass substrates and silicon. Spatters into the clean working space around the substrate.

  In the clean work space in the substrate processing process of LCD manufacturing, the temperature is precisely controlled and adjusted to the cleanliness class 10000 or less, the temperature is 23 ± 0.5 ° C, and the humidity is 40 ± 1.5%. Since it is indispensable to keep ammonia in a clean state of 0.2 ppb or less for organic substances and 2 ppb or less for organic substances, the air in which the above-mentioned molecular pollutants are scattered is immediately exhausted to adjust the temperature and humidity to the above conditions. It is installed so that it can be replaced with purified air.

  When molecular contaminants scattered in the clean work space collide and deposit on the substrate due to molecular motion, the substrate is contaminated and becomes a defective product. Therefore, it is assumed that the greater the number of molecules of the substance contained in the air, the higher the probability of deposition on the substrate.

  When removal is performed up to 0.2 ppb based on ammonia having the lowest molecular weight and the lowest boiling point, it is necessary to remove up to 1.2 ppb when HMDS is 2 ppb, TMS is 1.0 ppb, and the resist ink solvent is thinner.

  Conventionally, a one-pass disposable method has been adopted, but in this method, indoor or outdoor air is taken in to remove particulate and molecular contaminants, and temperature and humidity are adjusted. Since the temperature-controlled and humidity-cleaned air was supplied to the clean work space, and then the exhaust from the clean work space was treated as waste gas and then released to the atmosphere, a large amount of energy was consumed. I was consuming. However, recently, as the glass substrate increases in size, the clean work space also has a large capacity. Therefore, the exhaust from the clean work space is recovered, and particulate and molecular contaminants in the recovered processing air are collected. After removing and replenishing particulate and molecular pollutants in indoor or outdoor air for replenishment, the temperature and humidity are adjusted to clean and conditioned air, and circulated and supplied to the clean work space. It is being converted to a method that greatly reduces energy consumption.

(Chemical filter)
In the prior art, the aforementioned molecular contaminants are generally removed through a chemical filter installed in the vicinity of the outlet to the clean working space and in the circulating air duct (for example, Non-Patent Document 1). See). In particular, the chemical filter installed on the ceiling near the outlet is incorporated in a fan filter unit (FFU) in which a fan and a high-performance filter for removing particulate contaminants are integrated.
However, the increase in the size of the glass substrate described above increases the footprint (floor area) of the cleaning work space, and also increases the absolute amount of clean temperature-controlled and humidity-controlled air to be circulated. The number of chemical filters to be installed is increased because the chemical filter installed at the outlet to the cleaning work space is also large or needs to be supplied separately with purified temperature-controlled and humidity-controlled air.

Lecture materials hosted by the Semiconductor Industry Newspaper "Semiconductor clean technology has entered the Renaissance era" (held on February 21, 2007)

In the pollutant removal method using such a chemical filter, the above-mentioned molecular pollutants are basic and organic. Therefore, the chemical filter (B) for collecting and removing the basic substance and the organic substance are used. Two types of chemical filter (C) that collects and removes water are used.
Among them, the chemical filter (B) is a cloth filter material impregnated with an acidic agent, a fiber filter material added with a cation exchange group, or a cloth filter material sewed into a bag shape with pleats. A bag filled with a cation exchange resin is used.

  Therefore, the principle of collection / removal is to cause neutralization reaction of acid and base on the filter material to convert it into a non-volatile neutralized product. Therefore, basic contaminants exceeding the chemical equivalent of the basic substance that reacts with the amount of acidic substances impregnated in the filter material cannot be collected and removed. . For this reason, the chemical filter (B) that has reached the end of its life is unavoidable to replace it with a new one.

  The chemical filter (B) which has reached the end of its life by the replacement work becomes industrial waste, and the operation of the substrate processing process to which it has been attached is stopped during the replacement work. And the recent enlargement of the glass substrate increases the amount of industrial waste, and also increases the frequency of replacement.

  Furthermore, at the time of replacement, the clean work space, the clean air conduit, and related equipment are exposed to the atmosphere outside the process equipment. And since the atmosphere is clearly air containing more than 0.2 ppb of ammonia and more than 2 ppb of organic matter, the clean working space and clean air pipes that were in a clean state and related equipment to which they are connected, The inside of the equipment is also reliably contaminated. In particular, ammonia and water molecules tend to adsorb and adhere to the metal surface.

  Therefore, even if the replacement work is completed, a long-time cleanup work is required to restore the clean work space, the clean air conduit, and related equipment to a clean state. Loss due to shutdown during this period has caused enormous problems.

  Further, as described in the paragraph [0016], when the replacement operation is performed, for example, when exposed to clean room air containing 3 to 5 ppb of ammonia, the ammonia adsorbed and adhered to the metal surface will flow after the recovery. To desorb little by little and mix into the clean air stream. For example, if the ammonia concentration becomes 0.4 ppb due to desorption, it is considered that the probability of contaminating the glass substrate in the clean working space is doubled. Moreover, when water molecules in clean air condense on the metal surface or the like by molecular motion, the ammonia concentration in clean air becomes 0.2 ppb or more due to the rectification effect that ammonia molecules take away the heat of condensation and vaporize. .

  On the other hand, the chemical filter (C) that collects and removes organic substances is made by sewing a cloth-like filter material with pleats and sewing it into a bag shape and filling the bag with granular activated carbon, or activated carbon fiber. A filter material is used.

  Therefore, since the principle of collection / removal is to physically adsorb organic substances with high selectivity, the amount of organic pollutants exceeding the saturated adsorption amount of the packed activated carbon cannot be collected / removed. There is also a problem that a lifetime exists.

  That is, as in the case of the above-described chemical filter (B), the chemical filter (C) that has reached the end of its life is inevitable to replace it with a new one. The same problem as in paragraphs [0013] to [0017] described above occurs.

  Furthermore, when trying to clean the substrate processing process exhaust gas through the chemical filter (B) and the chemical filter (C), there are the following technical problems in addition to the essential problem that the lifetime exists. This will be described in detail below with reference to FIG. FIG. 5 is an explanatory diagram of a conventional cleaning apparatus.

  Prior to passing the processing air to the temperature and humidity control device 60, when exhausting the substrate processing step through the chemical filter unit 80 in which the chemical filter (B) 81 is disposed upstream and the chemical filter (C) 82 is disposed downstream, Ammonia and HMDS are collected and removed by a chemical filter (B) 81, and TMS, a resist ink solvent, and the like are collected and removed by a chemical filter (C) 82. These molecular contaminants are removed and cleaned, and then the pressure is increased by the processing air blower (2) 83 and flows into the temperature and humidity control device 60, and the particulate contaminants are removed by the high performance filter (4) 61. After the temperature and humidity is controlled by the removal and cooling dehumidifier 62, the temperature controller 63, and the humidifier 64, the pressure is again increased by the purified temperature and humidity controlled air blower 101 and the purified temperature and humidity controlled air supply port 2 Is inflated.

  According to the present inventors, the HMDS contained in the exhaust gas is hydrolyzed before and after being collected and removed by the chemical filter (B) 81, as shown by the following formula (2). In addition, ammonia and TMS are generated. The ammonia remains in the chemical filter (B) 81, but TMS is collected and removed by the chemical filter (C) 82.

(CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ + 2H ₂ O → NH ₃ +2 (CH ₃ ) ₃ SiOH (2)

  Since the adsorption capacity of organic gas is generally smaller than that of ammonia, the chemical filter (C) needs to use a large capacity. Even so, TMS can be removed at a high collection rate in the initial stage, but the collection rate gradually decreases. Therefore, in order to further collect and remove TMS, the high-performance filter (3) 114 and the filter fan 113 for removing the particulate contaminants installed in the clean temperature-controlled and humidity-controlled air outlet 115 of the clean work space 100. The chemical filter (C) 111 and the chemical filter (B) 112 are disposed in the fan filter unit (FFU) 110 in which the two are integrated. The chemical filter (B) 112 must be disposed because the phenomenon described in the following paragraph [0029] occurs.

Moreover, according to the present inventors, the TMS collected and removed by the chemical filter (C) 82 is further hydrolyzed and silica is adsorbed at the adsorption site as shown in the following formula (3). Since it is accumulated, thereafter, the adsorption site is blocked by silica and loses the adsorption performance. The generated methane (CH ₄ ) cannot be collected and removed by the chemical filter (C) 82 but is not a pollutant. Thus, the accumulation of silica raises the problem that the collection / removal rate of not only TMS but also other organic substances is rapidly reduced more than expected.

(CH ₃ ) ₃ SiOH + H ₂ O → 3CH ₄ + SiO ₂ ... (3)

  Further, since TMS has ionicity, the chemical filter (B) 81 disposed on the upstream side is also collected and removed at a low rate and hydrolyzed to accumulate silica. For this reason, since the active site in which the silica remained is deactivated, the collection / removal rate of ammonia and HMDS is reduced in accordance with the number of deactivated sites. Therefore, there has been a problem of greatly shortening the expected life assuming that ammonia is collected. Further, in order to collect the remaining ammonia that could not be collected by the chemical filter (B) 81, the chemical filter (B) 112 is further required. The present inventors have found that there is such a problem in the pollutant removal method using a chemical filter.

  Although not shown, when the chemical filter (C) 82 is disposed upstream and the chemical filter (B) 81 is disposed downstream to treat the exhaust of the substrate processing step, the TMS and the resist ink solvent are treated with the chemical filter (C 82), ammonia and HMDS are collected and removed by the chemical filter (B) 81.

  As described in paragraph [0026], TMS is hydrolyzed based on the formula (3), and silica accumulates at the adsorption site of the chemical filter (C) 82. Therefore, the adsorption site is blocked and deactivated. It will be. That is, the present inventors have found that the chemical filter (C) 82 causes an unexpected problem that not only the TMS but also the collection / removal rate of other organic substances decreases more rapidly than expected. . HMDS is also collected and removed by the chemical filter (C) 82, but is gradually hydrolyzed based on the formula (2).

  As the adsorption site of the chemical filter (C) 82 is blocked, HMDS and ammonia are collected and removed by the chemical filter (B) 81. Thereafter, HMDS undergoes hydrolysis to generate ammonia and TMS based on the formula (2). Ammonia stays in the chemical filter (B) 81, but molecular TMS generated twice as much as the generated molecular ammonia flows into the clean work space without being collected and removed, contaminating the space, substrate, pipes and equipment. Will do. Therefore, it is inevitable to further dispose the chemical filter (C) 111 downstream of the chemical filter (B) 81 as shown in FIG.

  Furthermore, as shown in the formulas (2) and (3), water is consumed by the hydrolysis reaction, and the ultrafine silica produced by the formula (3) adsorbs a large amount of water. When the filters (B) and (C) are installed downstream of the temperature and humidity control device, air having a predetermined relative humidity or less is supplied to the clean working space, resulting in a shortage of humidity control capability. Occur. As described above, the chemical filter has various problems.

(Batch temperature swing adsorption device)
Next, this occurs when the process air is passed through the humidifying / cooling / warming device of the present invention and then passed through a batch-type temperature swing adsorption device (hereinafter also referred to as “batch-type TSA device”) according to the prior art. The technical problem will be described with reference to the drawings. FIG. 4 is a block diagram of a batch type TSA apparatus 120 according to the prior art. FIG. 4 shows a case where the adsorption mode is the (A) system, and thus the regeneration mode is the (B) system.

  The processing air flows in from the processing air intake 41 and flows into the adsorbent unit (A) 43A from the branch / merging joint T1 through the on-off valve V1 and the branch / merging joint T2. The adsorbent unit (A) 43A adsorbs and removes basic pollutants and organic molecular pollutants.

  That is, the processing air is cleaned while passing through the adsorbent unit (A) 43A, and flows into the clean air outlet 50 through the branch / merging joint T3, the on-off valve V2, and the branch / merging joint T4. At this time, the on-off valves V1, V2 are in an open state, but the on-off valves V4, V5, V3, V6 are in a closed state.

  On the other hand, the regeneration air is taken from the regeneration air introduction port 51 and flows into the regeneration air heating unit 57. That is, the regeneration air passes through the regeneration air filter 58 and flows through the regeneration air blower 52, the regeneration air cooler 53, the regeneration air preheater 54, and the regeneration air heater 55. Subsequently, it flows into the adsorbent unit (B) 43B through the branch / merging joint T8, the on-off valve V7, and the branch / merging joint T5. During the heating time zone in the regeneration mode, the refrigerant of the heat transfer medium used for the regeneration air cooler 53 is not circulated, and the regeneration air heater 55 is energized.

  Therefore, since the adsorbent unit (B) 43B is heated by the regeneration air, a small amount of HMDS and a small amount of TMS such as ammonia and resist ink solvent adsorbed in the adsorption mode are desorbed. The regeneration air that has flowed out of the adsorbent unit (B) 43B flows into the regeneration air preheater 54 via the branch / merging joint T6, the on-off valve V8, and the branch / merging joint Т7. In the regeneration air preheater 54, the low temperature regeneration air is preheated by the excess heat of the high temperature regeneration air. The high-temperature regeneration air is cooled and discharged as exhaust air, and is discharged from the regeneration air discharge port 56.

  Further, during the cooling time zone in the regeneration mode, the refrigerant of the heat transfer medium is circulated through the regeneration air cooler 53 and the regeneration air heater 55 is not energized. Therefore, the adsorbent unit (B) 43B is cooled by the regenerated air and is brought close to the temperature of the processing air to prepare for switching to the adsorption mode. When the regeneration mode is the (B) system, the on-off valves V7 and V8 are in an open state.

  Thus, in a conventional batch-type TSA apparatus having two adsorbent units, if the adsorption and regeneration modes are executed simultaneously to continuously supply clean air, treated air, regenerative air, clean air, It is necessary to prevent the exhaust air from intermingling and connect (A) the system adsorbent unit (A) 43A and (B) the system adsorbent unit (B) 43B to the duct through which the air flows. Therefore, two ducts and processing air into which the processing air or exhaust air flows and the processing air are introduced upstream of the adsorbent unit, and the branch / joint joint T1 branches to the respective adsorbent units in the (A) system and (B) system. , The branch branch / merging joint T7 connected to the duct for guiding the exhaust air from the system (A) and the system (B) to the regeneration air discharge port 56, and the on-off valves V1, V4 for opening and closing the duct circuit on both sides, It is necessary to arrange V5 and V8.

  Further, on the downstream side of the adsorbent unit, two ducts through which clean air or regenerated air flows, and a duct connected to a duct leading to the clean air delivery port 50 from the (A) system duct and (B) the system duct are provided. Branch / joint joint T4, installed on both sides of the branch / joint joint T8 and each branch / joint joint that guides the regenerative air and sends it to the adsorbent units of (A) system and (B) system, and opens and closes the duct It is necessary to arrange the on-off valves V2, V3, V6 and V7 for this purpose.

  Further, branch / merging joints T2 and T6 are connected from the regeneration air duct to the (A) system duct so that the regeneration air flows from the (A) system duct to the exhaust air duct or (B) from the system duct to the exhaust air duct. Alternatively, branching / merging joints T3 and T5 are necessary so that the regeneration air flows from the regeneration air duct to the (B) system duct. Eventually, two systems on the upstream and downstream sides of the adsorbent unit (A) 43A and the adsorbent unit (B) 43B, a total of four ducts, a total of eight on-off valves, and a total of eight branch / merging joints is necessary.

This necessitates a “compulsion” of extremely complex and long ducts. Here, a duct used in an LCD factory, a semiconductor factory, or the like targeted by the present invention is not a small pipe having a diameter of about 50 mm. For example, a duct having a square cross section of 1000 mm. (In the case of a processing air amount of 500 m ³ / min, in order to flow at a flow rate of about 8 m / s, the dimension of the duct having a square cross section is 1000 mm.) Therefore, if this “pulling” is 30 m, An occupying space of 30.0 m ³ is required only with the duct. In the case where the amount of processing air is 40 m ³ / min, an occupying space of 8.7 m ³ is required only with the duct when the flow rate is about 8 m / s and the routing is 30 m.

  In other words, the space occupied by the duct through which the air under normal pressure flows is actually enormous, including the duct branch / merge joint, duct overlap, crossover, bending, expansion (reduction), open / close valve, heat insulation Since a space necessary for mounting the material is added, the occupied space as the whole apparatus becomes extremely large. This is the first reason why it is difficult to make a batch-type TSA apparatus having two adsorbent units compact.

  When switching the adsorption mode from the (A) system to the (B) system and the regeneration mode from the (B) system to the (A) system, the open / close valves V1, V2, V7 and V8 in the open state are closed. The on-off valves V4, V5, V3 and V6 in the closed state are switched to the opened state. Conversely, when switching the adsorption mode from the (B) system to the (A) system and the regeneration mode from the (A) system to the (B) system, the on-off valves V1, V2, V7 and V8 are opened from the closed state. The on-off valves V4, V5, V3 and V6 are switched from the open state to the closed state.

  Furthermore, switching between the adsorption mode and the regeneration mode allows the eight on-off valves with a small pressure loss and a large diameter to be started simultaneously and stopped simultaneously without stopping the flow of processing air and clean air. In addition, the operation time must be as short as possible.

  However, it is extremely difficult to start all the eight on-off valves at the same time, stop the operation at the same time, and operate them in a short time. If there is a slight delay in any of the on-off valves, there is a big problem that the flow rate and pressure of clean air fluctuate.

  If the flow rate and pressure of clean air fluctuate at the time of switching as described above, this is a major factor that significantly reduces the yield of LCD products.

  Still another problem is that, in the batch-type TSA apparatus according to the prior art shown in FIG. 4, when switching between the adsorption mode and the regeneration mode, the inside of the duct located between the eight branch / junction joints and the eight on-off valves. When the on-off valve is in the closed state, the flow of the air stops, so that it becomes a stagnation place where it remains as it is until the next valve opening. In FIG. 4, a duct that becomes a stagnation portion is indicated by a broken line.

  For example, the duct between the branch / merging joint T1 and the branch / merging joint T6, particularly the duct between the branch / merging joint T6 and the on-off valve V4 contains a high concentration of desorbed contaminants immediately after the start of regeneration. Since it becomes a stagnation place where the exhaust air stays, there is a problem that it affects the pollutant concentration in the clean air after switching.

  As already described in the paragraphs [0026] to [0031], the collection / removal rate of molecular contaminants with a chemical filter decreases with time, and it is necessary to replace them with new ones. As described above, the replacement with a new one causes the problem of the suspension of operation of the production equipment line due to the heavy work and the operation, and also the stoppage of the operation until the environmental problem of industrial waste and the clean state is restored. The problem of stop loss and the energy waste problem between them are generated at the same time. Further, with the generation of silica, the amount of expensive humidity control water and the energy for humidity control that vaporizes the water are suddenly changed, which causes a problem that humidity control is confused.

  On the other hand, if an attempt is made to maintain a certain amount of production, an extra production line must be installed, resulting in an increase in capital investment. In addition, the collection / removal rate of ammonia, TMS, and other organic substances by the chemical filter (B) and chemical filter (C) has a large effect on the product yield. Therefore, it is necessary to constantly monitor and secure and monitor personnel. The installation and installation of equipment is indispensable. This is a problem that cannot be overlooked.

  As is clear from the above description, there are a number of technical problems with the method of collecting and removing molecular contaminants to clean air using a chemical filter in the substrate processing process exhaust in LCD manufacturing. As a result, product cost increases, environmental problems and energy waste are induced, and development of a method for modifying a method using a chemical filter is inevitable.

  However, simply using a batch-type TSA apparatus according to the prior art requires an extremely complicated and long drawing duct and prevents the apparatus from being made compact, so enormous capital investment is inevitable. In addition, the difficulty of operating the four open / close valves from open to close and the other four open / close valves simultaneously from close to open, and the resulting flow and pressure fluctuations are unavoidable. In addition, there is a problem that a high concentration of molecular contaminants from the stagnation site is mixed into clean air, that is, a concentration variation problem of the molecular contaminants.

  On the other hand, there has been proposed an air cleaning device using an adsorbent rotor that can be used semipermanently and can be adsorbed and regenerated simultaneously using an adsorbent that can be regenerated without using a chemical filter. 263172).

  Although this proposal is not described in detail, there are the following problems. First, it is necessary to draw a long duct, and at the same time, since the cross section of the adsorbent rotor and the cross section of the duct are completely different, many joints having a complicated structure are required. Therefore, it is difficult to make a compact device. Second, it is impossible to prevent leakage of treated air, regenerated heated air, and regenerated cooling air from the sliding portion between the joint end surface and the adsorbent rotor end surface. Third, the adsorbent rotor must be divided into three zones: adsorption, regeneration, and cooling, each of which has different flow rates, flow rates, temperatures, pressures, flow directions, and contaminant quality and concentration. It is extremely difficult to prevent air, regenerative heating air, and regenerative cooling air from being mixed. Fourthly, the regenerative heating air and the regenerative cooling air flow continuously so that the energy consumption is large.

  The present invention has been made in view of the above-mentioned facts, when cleaning exhaust gas containing molecular contaminants discharged from a cleaning work space in a substrate processing step in LCD manufacturing or semiconductor manufacturing and supplying it in a circulating manner. The hexamethyldisilazane and trimethylsilanol contained in the exhaust gas are collected by the humidified water ejected from the two-fluid nozzle without stopping the operation of the manufacturing equipment line in the process, condensed in the cooler and hydrolyzed. After removing and adjusting temperature / humidity, a method of cleaning with adsorbent is provided, and a method for circulating and supplying purified temperature-controlled air to the cleaning work space continuously and stably over a long period of time is provided. Thus, the above-mentioned problem is to be solved.

[1] According to the present invention, two adsorbent units (A) and (B) are arranged in parallel, and an adsorption mode for adsorbing and removing air containing contaminants by the adsorbent unit (A) is performed. In parallel, the adsorbent unit (B) that has adsorbed the pollutants is desorbed by passing the heated regeneration air, and the adsorbent unit (B) is further cooled to perform a regeneration mode. Next, switching between the adsorption mode and the regeneration mode is performed, and an adsorption mode for adsorbing and removing air containing pollutants by the adsorbent unit (B) is performed. In (A), the heated polluted air is used to desorb the adsorbed contaminants, and further the cooling mode is used to perform a regeneration mode in which the adsorption mode and the regeneration mode are repeated alternately. Equipped with a device, said at those using air taken from the indoors or outdoors as regeneration air, a liquid crystal display manufacturing a substrate processing process contaminants substrate circulation supplying dampening cleaning temperature adjustment, adjust the exhaust gas containing a processing step exhaust a cleaning method, incorporated fogging warming device the exhaust as process air, to give a fogging warmed air, play mode which, using the intake air from the indoor or outdoor as regeneration air leading to the batch type temperature swing adsorption apparatus that has performed a method of cleaning a substrate processing process exhaust, characterized in that temperature adjustment, humidity and implementing the removal of molecular contaminants and particulate contaminants is provided The

[2] According to the present invention, the humidifying / cooling / heating apparatus according to [1] is obtained by using the measuring unit that measures the flow rate or flow rate, temperature, and related humidity of the processing air at the processing air introduction port. Calculation means to calculate the amount of humidified water required to saturate the treated air with moisture by humidifying and adiabatic cooling, installed in the pipeline through which the treated air flows, and the humidified water in the same direction as the flow Two-fluid nozzle for jetting air and air, a cooler installed downstream of the two-fluid nozzle, a heater installed downstream of the cooler, a humidifying water tank, an air compressor and a condensed water tank installed outside the pipe refrigerator unit, a device composed of piping connecting the humidification water pump and their actuated by the conversion control signal calculated value obtained using the arithmetic means and a liquid crystal disk as the humidification water Characterized by using a pure water or ultrapure water adapted to lay manufacturing (1) method of cleaning a substrate processing process exhaust according is provided.

[3] According to the present invention, in the humidifying / cooling / heating apparatus according to [1] or [2], hexamethyldisilazane and / or trimethylsilanol, which are contaminants contained in the processing air, are ejected from a two-fluid nozzle. The substrate processing process exhaust gas cleaning method according to [1] or [2], which is collected by humidified water, condensed by a cooler, hydrolyzed and removed.
In addition, it is preferable that the quality of the humidification water used with a humidification cooling heating apparatus has the purity of the pure water thru | or ultrapure water level suitable for liquid crystal display or LCD manufacture.

[4] According to the present invention, the cooler according to [2] -[3] has a function of controlling the temperature of the processing air flowing out of the cooler in a range of 4 to 17 ° C. The substrate processing process exhaust cleaning method according to [2] or [3] is provided.

[5] According to the present invention, the heater in [2]-[4] has a function of controlling the temperature of the processing air flowing out of the heater in a range of 15 to 30 ° C. A substrate processing process exhaust cleaning method according to any one of claims [2] to [4] is provided.

[6] According to the present invention, in [1]-[2], the batch-type temperature swing adsorption device (batch-type TSA device) using the air taken from the indoor or outdoor as regeneration air is a base in the treated air. System of adsorbent unit (A) in adsorption mode to remove organic molecular pollutants and organic molecular pollutants with adsorbent, and adsorb basic molecular pollutants and organic molecular pollutants The adsorbent unit (B) in the regeneration mode in which the adsorbent is cooled and heated by passing regeneration air is provided in parallel with two systems (A) and (B), and the regeneration air And a first air valve and a second valve which are switching means between the system (A) and the system (B) that alternately repeat the adsorption mode and the regeneration mode [1] ] Or [2] Method of cleaning a plate process exhaust gas is provided.

According to [7] The present invention, the adsorbent unit in [6] (A), (B), the adsorbent layer using those containing solid acidic material which selectively adsorbs basic molecular contamination and a substrate treatment process exhaust cleaning method according to [6], characterized in that it comprises a and an adsorbent layer b using activated carbon that selectively adsorbs organic molecular pollutants. Is provided.

[8] According to the present invention, in [6], the first valve and the second valve are internally partitioned into four small chambers by a frame-shaped partition plate, and each small chamber is rotated by the rotation of the plate-shaped rotating valve body. open and repeat closure, the adsorbent unit system and adsorbent unit (B) system characterized in that it is a 4-port auto-switching valves for switching the [6] of the substrate processing process exhaust description of the (a) A cleaning method is provided.

  According to the substrate processing process exhaust cleaning method of the present invention, ammonia, hexamethyldisilazane (HMDS), trimethylsilanol (TMS), resist ink in processing air can be used without using a chemical filter having many problems. All of the molecular contaminants such as solvents can be removed stably and continuously for a long period of time to 1 ppb or less. Therefore, it can contribute to the environmental improvement of drastically reducing industrial waste.

  In addition, according to the present invention, since no chemical filter is used, a serious work of replacing a chemical filter that has reached the end of its life with a new one becomes unnecessary, and there is no need to stop the operation of the substrate processing process to which the chemical filter is attached. In addition, it is possible to bring about a great economic effect of reducing the variable cost in the LCD manufacturing cost that the clean-up energy required for restoring the contaminated cleaning space to the clean state is also unnecessary.

  Furthermore, according to the present invention, since no chemical filter is used, an extra production line becomes unnecessary, and it is not necessary to monitor molecular pollutants such as ammonia, thereby eliminating the need for a monitoring device and personnel. A great economic effect of reducing the fixed cost in the manufacturing cost can be brought about.

  Furthermore, the substrate processing process exhaust cleaning method of the present invention can supply clean temperature-controlled air in a stable and continuous manner over a long period of time, thus contributing to an improvement in operation rate and product yield. be able to. Therefore, it can contribute to a significant reduction in the LCD manufacturing cost.

  In addition, according to the present invention, exhaust from the substrate processing process is taken as processing air to remove particulate pollutants and molecular contaminants, and to adjust the temperature and humidity, thereby providing a clean working space in the substrate processing process. Since it is supplied in a circulating manner, the temperature and humidity control energy for the clean work space in the substrate processing process can be significantly reduced compared to the enormous amount of energy required for temperature control and humidity control for large-capacity clean rooms.

  Further, in the present invention, since the regeneration air is used by taking in indoor air or outdoor air outside the system, almost all the exhaust of the substrate processing step taken in as processing air can be circulated and supplied to the clean work space as clean air. Therefore, the energy consumption can be greatly reduced as compared with a one-pass disposable cleaning temperature and humidity control apparatus.

  In the present invention, with respect to hexamethyldisilazane (HMDS) used in the substrate processing step and its decomposition products, ammonia and trimethylsilanol (TMS), utilizing the reactivity with water and the solubility in water, Prior to adsorption and removal of ammonia, resist ink solvent, etc., 20 μm or less using a two-fluid nozzle that ejects humidified water 1.0 to 1.2 times the amount of water necessary to saturate the processing air with moisture and compressed air The supersaturated state can be realized by humidified adiabatic cooling that generates a large number of mist droplets, and then condensed through a cooler, which can be removed efficiently and continuously.

  Further, in the present invention, since the high-performance filter (1) 15 (FIG. 2) is installed in the circulating air duct 104 (FIG. 1) and the exhaust from the substrate processing process is used as the processing air, the particulate contamination The concentration of the substance has already been extremely reduced, and the high-performance filter (2) 106 (FIG. 1) once attached can be used continuously over a long period of time. Further, even if the high-performance filter (1) 15, the dust removal filter (2) 102 (FIG. 1) and the dust removal filter (1) 12 (FIG. 2) are replaced, it is not necessary to stop the operation of the substrate processing step.

  The humidifying / cooling / heating apparatus in the present invention not only collects and removes HMDS and TMS, but further hydrolyzes it, and the cooler has a dew point temperature corresponding to the relative humidity required in the clean working space of the substrate processing step. Since it has a function to control and the heater has a function to control to a temperature required in the clean working space of the substrate processing step, conventionally, a chemical filter (FIG. 5) or an adsorbent rotor (patented) The temperature and humidity control device 60 (FIG. 5) installed downstream of the air purification device shown in the literature 1) is unnecessary, and energy saving and simplification of the system can be realized.

  In the present invention, an adsorption comprising a solid acid layer that can be repeatedly regenerated and adsorbs basic molecular contaminants with high selectivity and an activated carbon layer that adsorbs organic molecular contaminants with high selectivity. Since the material unit was used, ammonia was 0.2 ppb or less, HMDS was 2 ppb or less, TMS was 1.0 ppb or less, and various organic contaminants such as resist ink solvents were 0.2 ppb or less and 1.2 ppb or less, respectively. In addition, the cleanliness of the molecular contaminants required in the substrate processing process working space can be satisfied.

  In the present invention, the treatment air flowing into the adsorbent unit contains a very small amount of HMDS and TMS that deactivate the adsorption sites of the solid acid and activated carbon. Therefore, the adsorbent unit is continuously basic over a long period of time. Maintains the ability to adsorb and remove molecular contaminants and organic molecular contaminants.

  Since the batch type TSA apparatus in the present invention has the regeneration function with two adsorbent units in parallel (A) and (B), the adsorption mode and the regeneration mode are alternately used for the (A) system and the (B) system. By repeatedly switching the above, it is possible to clean the exhaust of the substrate processing process stably over a long period of time.

  The regeneration air used in the batch-type TSA apparatus of the present invention is indoor air or outdoor air outside the system, and is heated to 200 to 250 ° C. during the heating time period, so that the contamination remaining on the adsorbent after desorption. The adsorption equilibrium partial pressure of the substance is at a very low level.

  Since the batch type TSA apparatus according to the present invention includes the first valve and the second valve, which are four-port automatic switching valves, the flow to the clean working space may be intermittent when the adsorption mode and the regeneration mode are switched alternately. There is no pressure fluctuation.

  In addition, since the batch type TSA apparatus in the present invention does not have complicated ducting, the apparatus is compact, and there is no stagnation or stagnation between the duct and the valve. Even at normal and steady times, the concentration of molecular contaminants in clean air does not increase or fluctuate and is stable.

  In the present invention, both the humidifying water necessary for saturating the processing air and the humidity adjusting water necessary for conditioning the clean air are pure water or ultrapure water suitable for LCD production. Therefore, the yield of the LCD is kept high in the substrate processing process.

  The best mode for carrying out the present invention will be described below with reference to the accompanying drawings. FIG. 1 shows that exhaust from a substrate processing step in LCD manufacturing is taken as processing air from a processing air inlet 1 to adjust the temperature and humidity of the processing air and to remove molecular contaminants and particulate contaminants in the processing air. The present invention supplies purified temperature-controlled and conditioned air from the purified temperature-controlled and conditioned air supply port 2 to the cleaning work space 100 in the substrate processing step. It is a block diagram of this embodiment.

  In this figure, between the processing air introduction port 1 and the purified temperature control and humidity control air supply port 2, two devices, a humidification cooling and heating device 10 and a batch temperature swing adsorption device 40, are arranged in the order in which the processing air flows. Has been.

  Furthermore, the structure of the humidification cooling heating apparatus 10 was shown in FIG. In the humidification cooling heating apparatus 10, humidification cooling heating of processing air is performed. In FIG. 2, after the indoor air introduced from the indoor air inlet 11 is removed through the dust removal filter (1) 12, it is pressurized by the air compressor 13, and pure water or ultrapure water suitable for LCD manufacturing. Pure water is supplied as humidified water from the humidified water intake port 14, stored in the humidified water tank 18, and humidified water pressurized by the humidified water pump 17 is introduced from the processing air inlet port 1 to obtain a high performance filter (1 ) The two-fluid nozzle 16 installed in the pipeline through which the processing air that has passed 15 flows flows in the same direction as the processing air flow to atomize the humidified water. In the present embodiment, the humidified water is operated so as to be a mist droplet having an average body area diameter of 20 μm or less. At this time, the flow rate or flow rate at the processing air inlet 1, the temperature of the processing air, and the relative humidity are measured by the measuring means, and the measured values are input, and the amount of water required to saturate the processing air by humidified adiabatic cooling. The amount of humidified water 1.0 to 1.2 times the amount of water is calculated by the calculation means, and the humidified water pump 17 that is operated by the control signal obtained by converting the calculated value is installed so that water can be automatically supplied. Thus, since the processing air is adiabatically cooled as soon as the mist droplets are ejected from the two-fluid nozzle 16 and humidified, the temperature drops below the temperature at the processing air inlet 1 and becomes a saturated temperature. Since the moisture in the process air is in a supersaturated state, the supersaturated mist droplets do not disappear but reach the cooler 21 installed in the pipe along with the process air flow.

  In the practice of the present invention, pure water is used at the minimum, but ultrapure water is required in the field of LCD manufacturing, and the impurity content may be in the order of ppb or less. The water quality required for the field will be selected. In LCD production, it is preferable to use pure water or ultrapure water from which fine particles, viable bacteria, organic carbon, silica and the like are sufficiently removed in addition to the electrolyte directly related to the resistivity.

  In the embodiment of the present invention, as described above, mist droplets are generated using 1.0 to 1.2 times the amount of water necessary for saturation by humidified adiabatic cooling. Much more mist droplets than the number of droplets are generated, and the mist droplet diameter decreases because water evaporates from the unsaturation to saturation when the mist droplets are generated. Therefore, each mist droplet has a specific surface area larger than that in the unsaturated condition, and the surface area of the total number of mist droplets becomes enormous. In this way, the large number of mist droplets collide with contaminant molecules in the processing air between the two-fluid nozzle 16 and the cooler 21, take it into the mist droplets, and efficiently A state that can be collected can be realized. In particular, ammonia, HMDS, and TMS dissolved in water are dissolved in the mist droplets together with the collision, and reach the cooler 21 connected to the refrigerator unit 19 in a state of being dissolved in the mist droplets.

  The fog droplets reaching the cooler 21 and the supersaturated process air are further cooled to a set temperature selected from the range of 4 to 17 ° C. For this reason, the mist droplets that have reached the cooler 21 and the supersaturated portion of the water in the processing air are condensed to be condensed water and stored in the condensed water tank 22. At this time, ammonia has higher volatility than water (boiling point of ammonia: −33 ° C., boiling point of water: 100 ° C.), so that a rectification effect occurs in which water is condensed and ammonia is vaporized. 21 and reach the heater 31. Therefore, the removal rate of ammonia in the cooler 21 is lower than that of HMDS and TMS. Further, the water-insoluble organic substance reaches the heater 31 in the same manner as ammonia.

  Even when water condenses in the cooler 21, ammonia, HMDS, and TMS are collected in the water and stored in the condensed water tank 22. Therefore, ammonia, HMDS, and TMS are stored in the condensed water tank 22 together with the amount collected by the mist. Among these, ammonia is vaporized (volatilized) by the rectification effect as described above. On the other hand, HMDS and TMS are dissolved in condensed water. However, HMDS is hydrolyzed by the above formulas (2) and (3), and is decomposed into ammonia, methane, and silica. The other TMS is also hydrolyzed by formula (3) and decomposed into methane and silica. Hydrolysis according to the equations (2) and (3) also proceeds on the heat transfer surface of the cooler 21.

  Thus, since HMDS and TMS produce silica by hydrolysis, when the cleaning device of the present invention is operated for a long period of time, the silica becomes a scale on the surface of the cooler 21 or the inner surface of the condensed water tank 22. It adheres and reduces the heat transfer rate or closes the outlet of condensed water. For this reason, in the embodiment of the present invention, it is preferable to prevent the adhesion of the scale by coating those portions with, for example, a fluororesin.

The processing air flowing out of the cooler 21 is controlled to a set temperature selected from the range of 4 to 17 ° C., and is saturated with moisture having the dew point. Therefore, it is preferable to adjust the moisture corresponding to the relative humidity required in the clean work space. For example, when air having a temperature of 23 ° C. and a relative humidity of 45% is required in the clean work space 100, the water is adjusted to a moisture level that provides a relative humidity of 45% at a temperature of 23 ° C. by controlling the set temperature as 10.7 ° C. .
Next, the processing air is flowed into the heater 31 to raise the temperature. Since the processing air flowing out of the heater 31 is controlled to a set temperature selected from the range of 15 to 30 ° C., in the above example, by controlling the set temperature of the heater 31 as 23 ° C., the batch type The temperature is adjusted before flowing into the TSA device 40.

  The processing air that has flowed out of the warmer 31 is boosted to a pressure required to pass through the batch-type TSA device 40 by the processing air blower 32 and flows to the processing air intake 41. Next, the processing air flows into the adsorbent unit (A) 43A of the system (A) in the adsorption mode through the first valve 42 of the batch-type TSA device 40 shown in FIG.

  In the present invention, the adsorbent unit (A) 43A and the adsorbent unit (B) 43B are also added with a composite oxide composed of titanium and silicon, which is a solid acidic substance that selectively adsorbs a basic substance, or vanadium oxide and the like. The adsorbent layer “a” obtained by laminating a molded product prepared by processing the composite oxide into a honeycomb, corrugate, or pleat so that the pressure loss during ventilation is minimal, and selecting an organic substance Activated carbon, activated coke, graphite, carbon, activated carbon fiber, zeolite, etc., processed into a honeycomb, corrugated or pleated shape so that the pressure loss during ventilation is minimal, and then molded by firing The adsorbent layer b on which the objects are laminated is arranged in series and integrated.

  The processing air that has flowed into the adsorbent unit (A) 43A is a basic molecular pollutant while passing through the adsorbent layer a composed of a solid acidic substance that selectively adsorbs the basic substance. Ammonia and trace amounts of residual HMDS are removed, and while passing through the adsorbent layer b composed of activated carbon that selectively adsorbs organic substances, the resist ink solvent and the like that are organic molecular contaminants and trace amounts The remaining TMS and various remaining organic substances are removed.

  The treated air that has flowed out of the adsorbent unit (A) 43A becomes clean air in which ammonia is removed to 0.2 ppb or less, HMDS is 2 ppb or less, TMS is 1.0 ppb or less, and the resist ink solvent is 1.2 ppb or less. The air flows into the clean air outlet 50 through the air duct (A) 47, the second valve 45 and the clean air delivery duct 49.

  Next, in the present invention, the clean air thus obtained is introduced from the clean air outlet 50 to the purified temperature-controlled air blower 101 of FIG. 2 is supplied to the clean work space 100. As shown in FIG. 1, a high-performance filter (2) 106 for final adjustment of the cleanliness class is usually installed in the vicinity of the purified temperature-controlled and humidity-controlled air outlet 115 in the clean work space 100. In the vicinity of the air intake port, a dust filter (2) 102, an intake air fan 108, a circulation fan 103 for circulating the exhaust from the clean work space to the series of processing devices 10 and 40, and a circulation air duct 104 are installed. Has been.

  As the first valve and the second valve used in the batch-type TSA apparatus in the present invention, it is desirable to use a 4-port automatic switching valve created and proposed by the present inventors (see Japanese Patent Application Laid-Open No. 2006-300394). .

In detail, the present invention can be implemented by incorporating the contents of the publication.
In the embodiment of the present invention, the 4-port automatic switching valve used as the first valve and the second valve includes a housing portion having a space inside and a frame having an opening portion that divides the space portion into four small chambers. A partition-type partition plate, a plate-like rotary valve body that opens or closes the opening of the frame-type partition plate, an inflow port that constantly inflows gas existing in the four small chambers, and inflow and outflow of fluid alternately Inflow / outlet port (1) to be performed, outflow port to constantly flow out gas, inflow / outlet port (2) to alternately inflow and outflow of gas, and drive to rotate the plate-like rotating valve body around the rotation axis The member having a configuration including means, and the member forming the casing, the frame-shaped partition plate, the rotating shaft, and the plate-like rotating valve body are preferably valves having a heat insulating function. .

  In the embodiment of the present invention, such a 4-port automatic switching valve having the same shape, the same size, or the same function is used. Further, switching between the adsorption mode and the regeneration mode of the (A) system and the (B) system is performed by simultaneously operating the first valve and the second valve.

Here, the reproduction operation of the batch-type TSA apparatus according to the embodiment of the present invention will be described with reference to FIG. The regeneration mode is composed of a heating time zone and a cooling time zone. When the regeneration mode is in the heating time zone, the room temperature regeneration air taken from the regeneration air inlet 51 in FIG. The pressure is increased and flows into the regenerative air preheater 54 to regenerate the adsorbent unit, and recover the waste heat of the high-temperature regenerative air that leaves the adsorbent unit. Thereby, the regeneration air itself is preheated from normal temperature to 150 to 200 ° C. Next, the regeneration air flows into the regeneration air heater 55, is heated to 200 to 250 ° C. and flows out, and passes through the clean air duct (B) 48 from the second valve 45, and then the adsorbent unit (B) 43B in the regeneration mode. Flow into.
As a precaution, the regeneration air in the present invention refers to heated air that is sent to the adsorbent unit for which the adsorption mode has ended, and a process of desorbing impurities adsorbed from the adsorbent unit by the heated air ( This is the air used for the regeneration mode.

  The adsorbent is heated by the regeneration air heated to 200 to 250 ° C. flowing into the adsorbent unit (B) 43B, and adsorbed to the adsorbent at room temperature when the system (B) is in the adsorption mode in the previous cycle. Ammonia, resist ink solvent, and the like, and trace amounts of HMDS and TMS are desorbed and mixed in a stream of high-temperature regeneration air. At this time, ammonia and HMDS are adsorbed to the adsorbent layer a made of a solid acidic substance, and the resist ink solvent and TMS are adsorbed to an adsorbent layer b made of activated carbon. Be released.

  Since the molecular pollutants in the regenerated air used in the present invention are almost the same as those in the atmosphere, ammonia is 3 to 5 ppb, and organic molecular pollutants in which a very large number of components are detected by GC / MS analysis. Is 10 to 50 ppb in terms of hexadecane, and acidic molecular pollutants are mixed with 1 to 5 ppb of NOx and 0.1 to 0.5 ppb of SOx. Of course, HMDS, TMS, and resist ink solvents are below the detection limit. Since this is heated to a high temperature and used for desorption, the respective adsorption equilibrium partial pressures can be significantly reduced from the adsorption equilibrium partial pressure at normal temperature. In addition, since it is heated to 200 to 250 ° C., the volume flow rate of the regenerative air is increased from 1.60 times to 1.77 times that at room temperature due to thermal expansion, and the adsorbent as well as the heat energy necessary for desorption of the adsorbed substance A flow rate sufficient as the amount of regenerated air flowing in the bed can be given. That is, due to the desorption conditions of the present invention, the molecular contaminants in the adsorbent layer are thoroughly desorbed and discharged from the adsorbent unit.

  The regeneration air that has flowed out of the adsorbent unit (B) 43B is cooled to 60 to 70 ° C. by the regeneration air preheater 54 via the first valve 42 and at the same time is subjected to heat exchange to preheat the ambient regeneration air. It is discharged out of the system through the air discharge port 56. Normally, the regeneration air discharge port 56 is connected to a collective exhaust gas treatment device (not shown).

  Next, when the regeneration mode becomes the cooling time zone, the regeneration air boosted by the regeneration air blower 52 flows through the regeneration air preheater 54 and the regeneration air heater 55 and flows from the second valve 45 to the clean air duct (B ) 48 and flows into the adsorbent unit (B) 43B. When the regeneration mode is in the cooling time zone, the regeneration air heater 55 is not energized, so that the regeneration air that has flowed in remains at room temperature with the adsorbent unit (B) 43B, the first valve 42, the regeneration air preheater 54, It flows through the regeneration air discharge port 56. Naturally, at the time of switching from the heating time zone to the cooling time zone, the regenerated air at normal temperature is regenerated air preheater 54, regenerated air heater 55, second valve 45, clean air duct 48, adsorbent unit (B) 43B. The regeneration air preheater 54 and the regeneration air discharge port 56 flow while cooling. Note that when switching from the adsorption mode to the regeneration mode or from the regeneration mode to the adsorption mode, the batch-type TSA apparatus of the present invention can be operated even when the regeneration air is not supplied.

  When the (A) system or (B) system in the adsorption mode is switched to the regeneration mode, it becomes a heating time zone, and the regeneration air heater 55 is energized, so the regeneration air is the clean air duct (A) 47, The adsorbent unit (A) 43A, the regeneration air preheater 54, and the regeneration air discharge port 56 flow while being heated.

  When the adsorption mode is the (B) system, the regeneration mode is the (A) system, so that the processing air flows into the first valve 42 and the adsorbent unit (B) 43B to become clean air, and the second valve 45, The purified air flows in the order of the clean air outlet 50, and the regenerated air is a regenerated air inlet 51, a regenerated air blower 52, a regenerated air preheater 54, a regenerated air heater 55, a second valve 45, a clean air duct (A) 47, and an adsorbent. The unit (A) 43A, the first valve 42, the regeneration air preheater 54, and the regeneration air discharge port 56 flow in this order.

  In FIG. 3, the inner surfaces of the second valve 45 through which the clean air flows, the clean air duct (A) 47, the clean air duct (B) 48, the clean air delivery duct 49, and the clean air delivery port 50 are coated with, for example, fluororesin. Is preferred. However, it is desirable to attach a three-way valve whose inner surface is coated with fluororesin as the clean air outlet 50.

  By applying such a fluororesin coating, it is possible to prevent adhesion of ammonia and organic substances to the metal surface. Therefore, when performing a cleanup operation at the initial start or restart after the operation stop, the first valve 42 is used. And the operation of the processing air blower 32 and the regeneration air blower 52 are changed from the steady state conditions, and the heated regeneration air is passed from the second valve 45 to the clean air duct (A) 47. Can be cleaned up by passing from the second valve 45 through the clean air delivery duct 49 to the clean air delivery port 50 and from the second valve 45 to the clean air duct (B) 48. From when the steady state is entered, clean air that has flowed out of the adsorbent unit is mixed with ammonia and / or organic matter. It can be eliminated, and the clean-up work is completed in a short period of time.

  Although the above has described in detail that the silane coupling agent used in the substrate processing step is HMDS and TMS, it is not limited to HMDS, but various silane coupling agents or silylating agents such as γ -Organosilicon compounds such as aminopropylethoxysilane, methacrylsilane, vinylsilane, and silyl chlorides are used. In addition, various organosilicon compounds are used for silicone resin, silicone rubber material, silicone sealing material, silicone oil, silicone adhesive, and the like, which are constituent materials for clean room construction and manufacturing equipment.

At any point in time, these organosilicon compounds become decomposition products or monomers thereof and become molecular contaminants together with ammonia and hydrochloric acid and are mixed into the processing air. In the exposure process, SOx may be mixed as a molecular contaminant. In the embodiment of the present invention, the treatment air is purified because the common characteristic of organosilicon compounds such as reactivity with water or solubility in water can be used for cleaning to remove these molecular contaminants. Circulating supply to the clean work space as air is possible.
That is, in the present invention, a large number of fine mist droplets are generated using water in excess of the amount of water necessary for saturation by humidified adiabatic cooling, and the mist droplets collide with contaminant molecules in the processing air. In particular, ammonia, HMDS, and TMS, which are dissolved in water, can be removed by dissolving them in a mist droplet together with the collision.

  According to the substrate processing process exhaust cleaning method of the present invention, without using a chemical filter, molecular contaminants such as ammonia, hexamethyldisilazane (HMDS), and trimethylsilanol (TMS) in the processing air are removed. Any of them can be removed continuously and stably up to 1 ppb or less for a long period of time, which can contribute to the environmental improvement of drastically reducing industrial waste. In addition, the laborious work of replacing the chemical filter with a new one becomes unnecessary, and it is not necessary to stop the operation of the substrate processing process to which the chemical filter is attached, and it is necessary to restore the contaminated cleaning space to a clean state. Since the clean-up energy that has been used is no longer needed, industrial applicability is extremely high.

It is a block diagram of the cleaning apparatus in the embodiment of the present invention. It is explanatory drawing of the humidification cooling heating apparatus in this invention. It is a block diagram of the batch type TSA apparatus in this invention. It is explanatory drawing of the batch type temperature swing adsorption | suction apparatus in a prior art. It is explanatory drawing of the cleaning apparatus by a prior art.

Explanation of symbols

1: Process air introduction port 2: Purified temperature-controlled air supply port

10: Humidification cooling heating apparatus 11: Indoor air inlet 12: Dust removal filter (1)
13: Air compressor 14: Humidification water intake 15: High performance filter (1)
16: 2 fluid nozzle 17: humidification water pump 18: humidification water tank 19: refrigerator unit (1)

21: Cooler 22: Condensate tank

31: Heater 32: Process air blower

40: Batch type TSA device 41: Process air intake 42: First valve 43A: Adsorbent unit (A)
43B: Adsorbent unit (B)

45: Second valve

47: Clean air duct (A)
48: Clean air duct (B)
49: Clean air delivery duct 50: Clean air outlet 51: Regeneration air introduction port 52: Regeneration air blower 53: Regeneration air cooler 54: Regeneration air preheater 55: Regeneration air heater 56: Regeneration air discharge port 57: Regeneration Air heating unit 58: Regenerative air filter

60: Temperature control device 61: High performance filter (4)
62: Cooling dehumidifier 63: Temperature controller 64: Humidifier

80: Chemical filter unit 81: Chemical filter (B)
82: Chemical filter (C)
83: Process air blower (2)

100: Clean work space 101: Clean temperature-controlled humidity air blower 102: Dust removal filter (2)
103: Circulating air blower 104: Circulating air duct

106: High-performance filter (2)
107: Air intake 108: Intake air fan

110: Fan filter unit 111: Chemical filter (C)
112: Chemical filter (B)
113: Filter fan 114: High performance filter (3)
115: Clean temperature control humidity air outlet

120: Batch-type TSA device of the prior art

T1 to T8: branching / merging points V1 to V8: on-off valve

Claims (8)

Adsorbent units (A) and (B) are arranged in parallel, and an adsorption mode in which air containing contaminants is adsorbed and removed by the adsorbent units (A) is performed, and the contaminants are adsorbed in parallel. A regeneration mode is performed in which the adsorbed contaminants are desorbed by passing heated regeneration air through the adsorbent unit (B) and the adsorbent unit (B) is further cooled. Next, the adsorption mode and the regeneration mode are performed. The adsorbent unit (B) adsorbs and removes the air containing the pollutant, and in parallel, the adsorbent unit (A) that has adsorbed the pollutant is supplied with the regenerated air heated. A regenerative mode in which the adsorbed contaminants are desorbed by passing through and a regenerative mode for cooling is further provided, comprising a batch-type temperature swing adsorber that alternately repeats the adsorption mode and the regenerative mode. In those using air taken from the indoors or outdoors as a gas,
A substrate processing process exhaust purification method that cleans and adjusts and circulates exhaust containing pollutants in a substrate processing process of liquid crystal display manufacturing, and supplies the exhaust to the humidification cooling and heating apparatus as processing air intake, give the fogging warmed air, which, through the batch type temperature swing adsorption apparatus that has performed the playback mode using the intake air from the indoor or outdoor as regeneration air, temperature control, humidity DOO A substrate processing process exhaust cleaning method comprising removing molecular contaminants and particulate contaminants. The humidification cooling / warming device is a measuring means for measuring the flow rate or flow rate of the processing air at the processing air inlet, the temperature and the relative humidity, and the measurement value obtained by using the measuring means is inputted, and the processing is performed by humidification adiabatic cooling. Calculation means for calculating the amount of humidified water necessary to saturate the air with moisture, a two-fluid nozzle that is installed in a pipeline through which the treated air flows, and jets the humidified water and air in the same direction as the flow, the two fluids A cooler installed downstream of the nozzle, a heater installed downstream of the cooler, a humidifying water tank, an air compressor, a condensate water tank, a refrigerator unit installed outside the pipe, and the arithmetic means. a device composed of piping connecting the humidification water pump and their activated by control signals obtained by converting the calculated value, pure water or ultrapure water compatible with the liquid crystal display manufacturing as the humidification water Method of cleaning a substrate processing process exhaust claim 1, wherein be had.   In the humidifying / cooling / heating apparatus, hexamethyldisilazane and / or trimethylsilanol, which are contaminants contained in the processing air, are collected by humidified water ejected from a two-fluid nozzle and condensed and hydrolyzed by a cooler. 3. The method for cleaning exhaust of a substrate processing process according to claim 1, wherein the substrate processing process exhaust gas is removed. 4. The substrate processing process exhaust cleaning method according to claim 2 , wherein the cooler has a function of controlling the temperature of the processing air flowing out of the cooler within a range of 4 to 17 [deg.] C. . 5. The substrate processing step according to claim 2 , wherein the heater has a function of controlling the temperature of the processing air flowing out of the heater in a range of 15 to 30 ° C. 6. How to clean exhaust. The batch temperature swing adsorption device using the air taken from the indoor or the outdoor as the regeneration air is an adsorbent in an adsorption mode that removes basic molecular contaminants and organic molecular contaminants in the treated air with an adsorbent. System of unit (A) and adsorbent unit (B) in a regeneration mode in which the adsorbent adsorbing the basic molecular contaminants and organic molecular contaminants is cooled and heated by passing regeneration air through (A) and (B), the regeneration air heating unit for heating the regeneration air, and the adsorption mode and regeneration mode are alternately repeated. (B) The substrate processing process exhaust purification method according to claim 1 or 2, further comprising a first valve and a second valve which are switching means of the system. The adsorbent units (A), (B) selectively and adsorbent layer a, and the organic molecular contamination with those containing solid acidic material which selectively adsorbs basic molecular contamination The substrate processing step exhaust gas cleaning method according to claim 6, comprising: an adsorbent layer b using an activated carbon adsorbed on the substrate. The first valve and the second valve are internally divided into four small chambers by a frame-shaped partition plate, and the adsorbent unit (A) is repeatedly opened and closed by rotating the plate-like rotating valve body. 7. A substrate processing process exhaust cleaning method according to claim 6, wherein the system is a four-port automatic switching valve for switching between the system of (1) and the system of the adsorbent unit (B).

Images