JP2007194647A - Treatment device, and method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treatment device that achieves a reduction in device stop time by facilitating automation of replacement of an etchant. <P>SOLUTION: The treatment device includes an etching bath 3, which is provided with an overflow part 3a and in which a semiconductor wafer 1 is subjected to etching treatment by a hot phosphoric acid, a circulation filtration path part 5, which returns the phosphoric acid overflowed to the overflow part 3a into the etching bath 3 while filtering and heating it and adding pure water to it after leading it to the outside of the etching bath 3, a phosphoric acid regeneration device 6, which executes the regeneration treatment for executing heat treatment to the phosphoric acid extracted from the etching bath 3 while adding a hydrofluoric acid to it, replenishing piping 140a for replenishing the phosphoric acid regenerated with the phosphoric acid regeneration device 6 to the etching bath 3, and an etchant replacement means for replacing the whole quantity of the etchant on the basis of the number of times of the etching treatment while measuring the number of times of executing the etching treatment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  In the present invention, a silicon nitride film (hereinafter referred to as “nitride film”) such as a semiconductor wafer (for example, a silicon wafer, hereinafter referred to as “wafer”) is referred to as hot phosphoric acid (hereinafter referred to as “phosphoric acid”). In particular, the present invention relates to a processing apparatus having a regeneration unit that recovers phosphoric acid that has contributed to the etching process and makes it reusable.

In wafer processing in semiconductor manufacturing or the like, a fine nitride film pattern may be formed on a wafer by etching. In this etching, dry etching is mainly used, but an oxide film is selectively formed by using the formed nitride film as an oxidation mask, and the nitride film and the oxide film are etched to remove the unnecessary nitride film mask. A method of treating with hot phosphoric acid having a high selectivity is still widely used today. In this wafer processing, if etching is performed under a condition where the etching selectivity between the nitride film and the oxide film is large, the nitride film on the wafer reacts with water and decomposes into silicon oxide and ammonia, so that the etching is performed appropriately. In this reaction, it is known that phosphoric acid acts as a catalyst and can be used permanently as a catalyst by simply replenishing water without being consumed, and efficient etching is possible.
Japanese Patent Laid-Open No. 11-293479 Japanese Patent Laid-Open No. 11-186216 JP-A 61-182231 JP-A-9-45660

  However, in actual wafer processing, in order to increase the etching selectivity, it is unavoidable to use the decomposed silicon oxide dissolved in hot phosphoric acid at a high concentration. The amount reaches the saturation dissolution amount and the silicon oxide precipitates as fine particles, which become fine particles that contaminate the wafer and clog the circulating filter for reusing the etchant. Cause various obstacles. Therefore, before the dissolved amount of silicon oxide reaches the saturated dissolved amount, for example, the etching solution must be replaced with new phosphoric acid or the concentration of silicon oxide in phosphoric acid must be lowered. Phosphoric acid containing a large amount of silicon oxide cannot be used as an etching solution and must be disposed of as a waste solution, which may adversely affect the environment.

  Further, the etching rate of the nitride film mask is constant regardless of the silicon oxide concentration if the phosphoric acid temperature is constant, but the etching rate of the oxide film is inversely proportional to the silicon oxide concentration in phosphoric acid, and the silicon oxide concentration increases. Decrease. As described above, since the etching selectivity between the nitride film and the oxide film changes according to the silicon oxide film concentration, the oxide film thickness varies among the processing lots, resulting in quality degradation. Therefore, it is necessary to increase the design and processing margin of the wafer processing apparatus by that amount, but the allowable margin has decreased with the progress of IC miniaturization and high integration. From such a background, it is desired to realize a wafer processing apparatus that has a high selection ratio, little variation between processing lots, and that does not discharge phosphoric acid waste liquid.

  The present applicants have developed a wafer processing apparatus structure and a regeneration method such as Japanese Patent Application Laid-Open Nos. 11-293479 and 9-45660 from the above situation. The present invention further improves them, and aims to facilitate the automation of the etching solution replacement, to shorten the stop time of the apparatus, and to reduce or maintain the impurities in phosphoric acid. Yes. Then, the etching selectivity between the nitride film and the oxide film is kept high, and the nitride film can be etched with phosphoric acid with a constant selectivity.

  The processing apparatus of the present invention includes an etching tank with an overflow portion that etches a semiconductor wafer with hot phosphoric acid, and the phosphoric acid overflowing the overflow portion is led out of the etching tank, filtered, heated, and added with pure water. A circulation filtration path section that returns to the inside of the etching tank, and a phosphoric acid regenerator that recovers the phosphoric acid that has been subjected to the etching treatment and performs a heat treatment by adding hydrofluoric acid to the phosphoric acid, and the phosphoric acid regenerator. A replenishing pipe for replenishing the regenerated phosphoric acid to the etching tank; and an etchant exchanging means for measuring the number of times the etching process is performed and exchanging the total amount of phosphoric acid based on the number of times of the processing.

  According to the processing apparatus of the present invention, the phosphoric acid in the etching tank can be exchanged all at once. Thereby, when phosphoric acid is replenished to the etching tank, the time for stopping the apparatus for adjusting the concentration and temperature can be shortened. The processing apparatus of the present invention can take the following modes, for example.

  (A) In the treatment apparatus of the present invention, the phosphoric acid regenerating apparatus comprises a receiving tank for temporarily storing the recovered phosphoric acid, a treatment tank for adding and heating hydrofluoric acid to phosphoric acid introduced from the receiving tank, and the treatment A storage tank that temporarily stores the phosphoric acid regenerated in the tank, the processing tank is a cooler that cools and liquefies the vapor evaporated from the processing tank, and the liquid liquefied by the cooler is constant. The thermostat can be adjusted to a temperature, and a measurement unit including a fluorine measuring unit that measures the fluorine concentration in the liquid adjusted in the thermostat.

  (B) In the processing apparatus of the present invention, the replenishment pipe may include a new liquid supply unit that supplies new phosphoric acid to the etching tank.

  (C) In the treatment apparatus of the present invention, the circulation filtration path section has a branch pipe before the filtration section for filtering phosphoric acid, and the phosphoric acid regeneration apparatus according to the circulating fluid pressure of phosphoric acid flowing to the filtration section Means can be provided for controlling the amount of phosphoric acid introduced to the side.

  (D) In the processing apparatus of the present invention, the replenishment pipe can switch between a route for sending the regenerated phosphoric acid taken out from the storage tank to the etching tank or the overflow section, and a circulation path for returning it to the storage tank again. Can be configured.

  (E) In the treatment apparatus of the present invention, the storage tank has heating means for controlling the regenerated phosphoric acid introduced from the treatment tank to a predetermined temperature, and between the overflow section, Can be connected with supply piping.

  (F) In the treatment apparatus of the present invention, the storage tank has heating means for controlling the regenerated phosphoric acid introduced from the treatment tank to a predetermined temperature, and between the circulation filtration path section. It can be connected by the supply pipe.

  (G) In the processing apparatus of the present invention, the heating means can be controlled by the timing of supplying the regenerated phosphoric acid from the storage tank to the etching tank.

  (H) In the treatment apparatus of the present invention, the treatment tank has a circulation path for circulating phosphoric acid in the tank, and the circulation path can have a filtration part.

  (I) The processing apparatus of this invention can be used for the manufacturing method of a semiconductor device.

  Hereinafter, the present invention will be described with reference to the drawings showing the embodiments. FIG. 1 is a block diagram mainly showing an etching tank and a circulation filtration path portion in the apparatus of the present invention, and FIG. 2 is a block diagram mainly showing a phosphoric acid regenerating apparatus in the apparatus. In the following description, after describing each part of the device of the present invention, an example of device operation will be described.

(Device structure)
This processing apparatus is mainly composed of an etching unit 4, a circulation filtration path unit 5, and a phosphoric acid regeneration device 6. The etching unit 4 is a portion where a plurality of wafers 1 are stored in the wafer cassette 2 and immersed in hot phosphoric acid (etching solution) to etch the nitride film of the wafers 1. The circulation filtration path part 5 is a part where the phosphoric acid overflowed from the etching tank 3 is returned to the etching tank 3 again through the filtration, heating, and pure water addition steps. The phosphoric acid regenerator 6 branches the phosphoric acid from the circulation filtration path 5 to lower the silicon oxide concentration in the phosphoric acid, regenerates the phosphoric acid with a certain silicon oxide concentration usable in the etching solution, and overflows the etching tank 3. This is the place to return to the flow part 3a.

a. Etching Unit In this etching unit 4, an automatic transfer robot (not shown), a belt conveyor, and the like are arranged together with the etching tank 3, and the wafer 1 is taken in and out of the tank body of the etching tank 3 and is subjected to an etching process. In the etching tank 3, the tank body is defined by the inner peripheral wall 30 and the bottom wall 31, and an overflow portion 3 a that receives phosphoric acid overflowing from the upper end of the inner peripheral wall 30 is formed on the outer periphery. The inner peripheral wall 30 and the bottom wall 31 are provided with a surface heater which is a heating element (not shown). The tank body is provided with a mesh 32 which is a dispersion plate inside the bottom, and the wafer cassette 2 is held on the mesh 32.

  The liquid introduction / discharge structure circulates the replenishment port 33 for replenishing phosphoric acid (mainly regenerated phosphoric acid) provided on the upper side of the overflow part 3a and the overflowed phosphoric acid provided on the bottom wall of the overflow part 3a. A discharge port 34 for discharging to the filtration path 5, a supply port 35 for introducing phosphoric acid provided in the bottom wall 31 and treated in the circulation filtration path 5 into the tank body, and similarly provided on the bottom wall 31. A discharge port 36 for discharging the entire amount of the liquid in the etching tank 3 is provided.

  As the control system, the liquid level sensor 37 for detecting the amount of phosphoric acid in the etching tank 3, the temperature sensor 38 for detecting the liquid temperature of phosphoric acid in the tank body, and the temperature detected by the temperature sensor 38 are described above. A heater controller 39 is provided for controlling the surface heater to maintain phosphoric acid at a constant predetermined temperature.

b. Circulation Filtration Path Unit The circulation filtration path unit 5 is provided with a pump 50 and a filter 51 that is a filtration unit. The phosphoric acid discharged from the discharge port 34 of the overflow portion 3 a is returned to the tank body of the etching tank 3 from the supply port 35 by the pump 50 and filtered through the filter 51. The circulation filtration path unit 5 includes a line heater 52, a temperature sensor 53, a heater controller 54, and a metering pump 55 for supplying pure water. The line heater 52 maintains the filtered phosphoric acid at a constant predetermined temperature, and is controlled by a temperature sensor 53 and a heater controller 54. Then, a predetermined amount of pure water is added to the phosphoric acid heated to the constant temperature by the metering pump 55. That is, here, phosphoric acid is first filtered by the filter 51 with respect to the etching solution, that is, phosphoric acid discharged from the overflow portion 3a. Next, phosphoric acid is heated to a certain temperature by the line heater 52, and then purified water is added by the metering pump 55 to adjust the phosphoric acid concentration to be kept constant, and returned to the tank body.

c. Phosphoric acid regenerating apparatus The phosphoric acid regenerating apparatus 6 is mainly composed of a receiving tank 70, a processing tank 100, and a storage tank 130. The phosphoric acid regenerating apparatus 6 regenerates phosphoric acid that has been subjected to etching, and supplies the regenerated phosphoric acid to the etching unit 4. It is a place.

  A discharge pipe 60 is connected between the receiving tank 70 of the phosphoric acid regenerating apparatus 6 and the discharge port 36 of the etching tank 3. The discharge pipe 60 is provided with an automatic valve 61. When the automatic valve 61 is opened, the phosphoric acid in the tank is discharged.

  Further, a branch pipe 62 is provided between the pump 50 and the filter 51 of the circulation filtration path unit 5. The branch pipe 62 is provided with a pressure gauge 63, a needle valve 64, and an automatic valve 65. Here, the pressure gauge 63 measures the fluid pressure (circulation fluid pressure or filtration pressure) before the filter 51, that is, the piping portion between the pump 50 and the filter 51. The needle valve 64 is a flow rate adjusting valve. By appropriately adjusting the opening degree of the needle valve 64, the flow rate of phosphoric acid branched from the branch pipe 62 is automatically set in accordance with the circulating fluid pressure. Controlled. The automatic valve 65 is an on-off valve. When the automatic valve 65 is open, the phosphoric acid branched from the branch pipe 62 is collected in the receiving tank 70.

  The receiving tank 70 has a plurality of liquid level sensors 71, and always measures the recovery amount. The measured data is transmitted to the control circuit 300 described later, and the control circuit 300 controls the opening and closing of the automatic valve 101 based on the collection amount. That is, when the amount of phosphoric acid in the receiving tank 70 reaches a predetermined amount, the automatic valve 101 is opened, and phosphoric acid is introduced into the treatment tank 100 from the discharge port 72 at the bottom.

  The processing tank 100 is configured in a set with the measurement unit 7. The treatment tank 100 is provided with a liquid level sensor 102, a surface heater 103, a surface heater 104, and the like, a temperature sensor 105, and a heater controller 106. The phosphoric acid in the tank is adjusted by the heater controller 106 controlling the surface heaters 103, 104 and the like based on the temperature detected by the temperature sensor 105. Further, the processing tank 100 has a metering pump 107 which is a pure water supply means for adding pure water into the tank, a supply pipe 108 in the tank, and a chemical solution supply for supplying a necessary amount of HF (hydrofluoric acid, that is, hydrogen fluoride). An HF tank 109 and a metering pump 110 as means are provided.

  As a liquid introduction / discharge structure, a supply port 112 for supplying HF, a supply port 114 for introducing phosphoric acid from the receiving tank 70, and vapor necessary for the measurement unit 7 are provided in the upper part of the processing tank 100. A steam outlet 113 is provided for extraction. At the bottom of the treatment tank 100, a discharge port 115 for discharging phosphoric acid is provided.

  The discharge port 115 is provided with a filtration pipe 116, and the filtration pipe 116 is provided with an automatic valve 117, a pump 118, a filter 119, and a heater 120. That is, the phosphoric acid discharged from the discharge port 115 is returned to the treatment tank 100 from the supply port 112 by the pump 118, filtered through the filter 119 that is a filtering unit, and heated by the heater 120. A branch pipe 121 is provided in the filtration pipe 116. The branch pipe 121 is provided with an automatic valve 122, and the phosphoric acid that has been regenerated is discharged to the storage tank 130 through the branch pipe 121.

  In this manner, by providing the filter 119 in the filtration pipe 116, foreign substances and particles in the regenerated phosphoric acid can be removed.

  The measuring unit 7 is a part for detecting the current concentration of hydrofluoric acid introduced into the phosphoric acid in the treatment tank 100 for regeneration and determining the progress and end point of regeneration. In this embodiment, a cooler 200 that cools the vapor of the processing bath 100, a thermostatic chamber 201 including a spiral tube that adjusts the liquid cooled here to a constant temperature, its temperature controller 202, and the liquid from the thermostatic bath 201. In order to calculate the fluorine concentration of phosphoric acid in the treatment tank 100, a conductivity meter 205 having a conductivity sensor 204 that measures the conductivity of the liquid in the heat retention vessel 203 is provided. Since the heat retaining container 203 here uses the conductivity sensor 204, a container having a certain depth is used. Further, the fluorine concentration in the phosphoric acid in the treatment tank 100 is calculated and processed by a control circuit (such as a microcomputer) 300 which is the main control means of the apparatus based on the conductivity data measured by the conductivity meter 205. Calculated. The control circuit 300 calculates the input amount of hydrofluoric acid and pure water according to the amount of phosphoric acid in the treatment tank 100, controls the metering pumps 110 and 107 to satisfy each calculated input amount, and controls the fluorine concentration. When the value becomes less than the specified value, the end of regeneration is notified, the automatic valves, needle valves, metering pumps, etc. of each part described above are controlled as necessary, and necessary signals are exchanged with the heater controller, etc. of each part. The entire wafer processing apparatus is controlled by giving and receiving.

  The storage tank 130 is a place where the phosphoric acid regenerated in the processing tank 100 is stored in a batch manner via the branch pipe 121 and the regenerated phosphoric acid is replenished to the overflow part 3a via the replenishment pipe 140a.

  The storage tank 130 includes a surface heater 131 and a surface heater 132, a liquid level sensor 133, a temperature sensor 134, and a heater controller 135. The surface heater 131 and the surface heater 132 heat the stored regenerated phosphoric acid to a predetermined temperature, the temperature sensor 134 detects the temperature of phosphoric acid in the tank, and the heater controller 135 detects the surface heater based on the detected temperature. 131 and the surface heater 132 are controlled. Moreover, the storage tank 130 can be equipped with the metering pump 136 which is a pure water supply means which adds a pure water in a tank, and the replenishment piping 137 in a tank.

  Conventionally, the phosphoric acid that has been regenerated has been introduced into the etching tank 3 without being adjusted in concentration or temperature. Therefore, after being introduced into the etching tank 3, it is necessary to adjust the concentration and temperature. There was a problem that the stop time was long. However, according to the present invention, since the storage tank 130 is provided with heating means and pure water supply means, the temperature and concentration are set to conditions suitable for processing in the process in advance before being introduced into the etching tank 3. Can be adjusted. The phosphoric acid adjusted in this way can be processed immediately after being supplied to the etching tank 3, and the downtime of the apparatus can be shortened.

  The heating means can be controlled in accordance with the timing of supplying the regenerated phosphoric acid to the etching tank 3. For example, when the heating means is used only immediately before supplying the regenerated phosphoric acid to the etching tank 3, unnecessary power consumption can be prevented.

  The storage tank 130 and the overflow part 3a are connected by a replenishment pipe 140a provided with an automatic valve 143 and a needle valve 144 on the overflow part 3a side. The supply pipe 140 a is provided with a circulation pipe 140 b that branches upstream from the automatic valve 143. That is, when the automatic valve 143 is closed, the phosphoric acid is returned to the storage tank 130 through the supply pipe 140a and the supply pipe 140b and circulated. Then, as described above, signals are transmitted from the control circuit 300 to the pump 141 and the needle valve 144 based on the detection result of the liquid level sensor 37 in the etching tank 3, thereby regenerating the phosphoric acid in the storage tank 130. Is supplied to the overflow part 3a. In addition, a new liquid supply unit 8 is provided in the supply pipe 140a. Specifically, in the supply pipe 140a, a branch pipe 150 is provided between the needle valve 144 and the supply port 33 of the etching tank 3, and the branch pipe 150 connects the supply pipe 140a and a new phosphoric acid tank 153. is doing. The branch pipe 150 is provided with a pump 152 and an automatic valve 151, and a new phosphoric acid solution is supplied through the branch pipe 150 as necessary.

(Device operation)
Next, an outline of an operation or operation example of the above wafer processing apparatus will be described.

  First, when the nitride film-formed wafer 1 is placed in the wafer cassette 2 and placed in the etching bath 3 filled with heated phosphoric acid, the nitride film on the wafer 1 is etched by the hot phosphoric acid. The In this treatment process, hot phosphoric acid overflowing from the main body of the etching tank 3 is collected in the overflow portion 3 a, discharged from the discharge port 34 to the circulation filtration path portion 5, and sent to the filter 51 side by the pump 50. The phosphoric acid that has passed through the filter 51 is heated to a desired temperature (for example, the temperature just before the boiling point of phosphoric acid) by the line heater 52, and a predetermined amount of pure water is added to the heated phosphoric acid via the metering pump 55. Then, it is sent from the supply port 35 into the main body of the etching tank 3 and circulated. In this way, since phosphoric acid is circulated in the etching tank 3, the nitride film of the wafer 1 is appropriately etched.

  In this etching process, the number of times the etching process is performed is measured, and when the number of processes reaches a predetermined number, the phosphoric acid in the etching tank 3 is replaced. The number of etching processes is performed, for example, by measuring the loading / unloading of the wafer cassette 2. When the number of treatments reaches a predetermined number, the control circuit 300 opens the automatic valve 61 and the entire amount of phosphoric acid in the tank is discharged and collected in the receiving tank 70.

  Next, after the total amount of phosphoric acid in the tank is discharged, the automatic valve 61 is closed by a signal from the control circuit 300, the automatic valve 143 of the replenishing pipe 140a is opened, and the storage tank 130 to be described later is regenerated. Phosphoric acid is supplied. At this time, the amount of phosphoric acid supplied is measured by the liquid level sensor 37, and the automatic valve 143 is closed based on the result. In this manner, in the etching tank 3, phosphoric acid that has undergone a predetermined etching process can be exchanged with phosphoric acid having a low silicon oxide concentration.

  When supplying phosphoric acid to the etching tank 3, new phosphoric acid is supplied from the new liquid supply unit 8 as necessary. For example, when phosphoric acid is insufficient in the storage tank 130, the control circuit 300 opens the automatic valve 151 and new phosphoric acid is supplied through the branch pipe 150.

  Therefore, in this structure, when the number of treatments reaches a predetermined number, the free time of the etching solution apparatus can be reduced by replacing the total amount of phosphoric acid in the tank. Also, in the etching process until the next replacement, a part of phosphoric acid having a silicon oxide concentration higher than a predetermined concentration is discharged and replenished with phosphoric acid having a low silicon oxide concentration. The concentration can be maintained at an optimum state. Further, in the circulation filtration path section 5, in order to discharge a part of phosphoric acid having a high silicon oxide concentration in order to maintain the concentration of phosphoric acid suitable for the process processing until the next replacement of the etching solution, the branch pipe 62 is provided. Is provided. The branch pipe 62 is provided with a pressure gauge 63, and the pressure gauge 63 measures the circulating fluid pressure before the filter 51. When the concentration of silicon oxide in phosphoric acid increases, the amount of silicon oxide deposited on the filter 51 increases, so that the circulating fluid pressure increases. That is, the silicon oxide concentration of phosphoric acid can be predicted by measuring the circulating fluid pressure. The pressure value (circulation fluid pressure) measured by the pressure gauge 63 is transmitted to the control circuit 300, and if the measurement result is equal to or greater than a predetermined value, the control circuit 300 opens the automatic valve 65 and the circulation filtration path. Part of the phosphoric acid flowing through the section 5 is collected into the receiving tank 70 via the branch pipe 62.

  As described above, when a part of phosphoric acid is recovered from the circulation filtration path portion 5 and the phosphoric acid in the etching tank 3 is reduced, the control circuit 300 opens the automatic valve 143 of the supply pipe 140a and opens the storage tank 130. Regenerated phosphoric acid is replenished.

  In this case, since the regenerated phosphoric acid in the storage tank 130 is regenerated in the treatment tank 100 and has a low silicon oxide concentration, the silicon oxide concentration in the phosphoric acid in the etching tank 3 can be maintained at a low value accordingly. . Further, in the circulating filtration path section 5, since the phosphoric acid having a low silicon oxide concentration is sent from the pump 50 to the filter 51 side, the deposited silicon oxide on the filter 51 is redissolved and removed. An advantage of this is that the deposited silicon oxide of the filter 51 is redissolved because the phosphoric acid has a low silicon oxide concentration, so that the filter 51 can be used for a long period of time.

  In the receiving tank 70, the data measured by the liquid level sensor 71 is transmitted to the control circuit 300, and the control circuit 300 controls the automatic valve 101 based on the measured data. That is, when the phosphoric acid in the receiving tank 70 reaches a predetermined amount, the automatic valve 101 is opened, and the phosphoric acid in the receiving tank 70 is collected into the processing tank 100.

  The phosphoric acid collected in the treatment tank 100 is discharged from the discharge port 115 and circulated through the filtration pipe 116 during the regeneration process. As described above, the phosphoric acid in the treatment tank 100 is circulated through the filtration pipe 116 and passes through the filter 119 as a filtration unit, whereby impurities and particles in the phosphoric acid can be removed.

  In this regeneration process, an appropriate amount of hydrofluoric acid in the HF tank 109 is supplied into the processing tank 100 by the metering pump 110, and pure water is supplied into the processing tank 100 through the pure water supply pipe 108 by the measuring pump 107. The For the supply amount of the hydrofluoric acid and pure water, see, for example, the relevant part of JP-A-11-293479. In this regeneration process, the surface heaters 103 and 104 are controlled to increase the liquid temperature in the processing tank 100, and the evaporated vapor is led from the vapor extraction port 113 to the cooler 200 to be cooled and returned to the liquid. This liquid passes through the spiral tube in the thermostat 201 and flows into the heat retaining container 203 while being adjusted to a constant temperature. It should be noted that new liquid always flows into the heat retaining container 203 so that old liquid does not accumulate. Necessary processing is performed on the liquid flowing out of the heat insulating container 203.

  Subsequently, the conductivity of the liquid in the heat retaining container 203 is measured by the conductivity meter 205 (conductivity sensor 204), and the measured data is stored in the storage unit of the control circuit 300. In the control circuit 300, the data is arithmetically processed to calculate the fluorine concentration, the time when the fluorine concentration becomes a conductivity corresponding to a desired value is determined, and the silicon oxide concentration in the phosphoric acid in the treatment tank 100 is a predetermined value. Determine when it is lower. The phosphoric acid in the treatment tank 100 is added with the above-mentioned hydrofluoric acid and added with pure water, so that the silicon oxide concentration in the phosphoric acid is lowered, and this phosphoric acid can be used for etching the nitride film of the wafer 1. When the concentration is reached, the automatic valve 122 is opened according to a command from the control circuit 300 and discharged to the storage tank 130. The phosphoric acid in the storage tank 130 is detected by the liquid level sensor 133, and the opening time of the automatic valve 122 is controlled based on the detection result.

  The phosphoric acid in the storage tank 130 is maintained at a predetermined temperature (for example, a temperature one step before the boiling point) by the surface heaters 131 and 132, and when replenished to the overflow part 3a, the circulation filtration path part 5 and the main body of the etching tank 3 It is processed so as not to cause a temperature drop of phosphoric acid. And in the replenishment to the overflow part 3a, based on the detection result of the liquid level sensor 37 of the etching tank 3, the automatic valve 143 is made into an open state, and the phosphoric acid in the storage tank 130 is pump 141, automatic valve 143, and Supplied through a needle valve 144. In addition, the phosphoric acid in the storage tank 130 is normally circulated from the replenishment piping 140a through the needle valve 142 and the circulation piping 140b. For example, the needle valve 142 is controlled so that the valve opening is minimized only when replenishing the overflow portion 3a. This is to maintain the phosphoric acid temperature in the storage tank 130 as constant as possible.

  At this time, the measurement results of the liquid level sensor 133 and the temperature sensor 134 of the storage tank 130 are transmitted to the control circuit 300, and when the amount of phosphoric acid is insufficient, the automatic valve 151 of the new liquid supply unit 8 is used. Is opened and new phosphoric acid is supplied.

  In addition, the phosphoric acid in the storage tank 130 can be heated in accordance with the timing of supplying the liquid to the etching tank 3 in addition to being heated as described above. In this method, in particular, when the etching process is completed a predetermined number of times in the etching tank 3 and the entire amount of the etching solution is replaced, the timing of supplying the etching tank 3 is known in advance. It can prevent wasteful heating and reduce power consumption.

  Further, in the storage tank 130, the concentration and temperature of phosphoric acid in the tank are adjusted by adding pure water through the metering pump 136 and the replenishment pipe 137, so that the same condition as that of phosphoric acid used in the process is obtained. it can. As a result, the phosphoric acid in the storage tank 130 can start the process immediately after being supplied to the etching tank 3.

  As described above, in this structure, the fluorine concentration in the phosphoric acid in the treatment tank 100 is measured without being affected by temperature change or carbon dioxide in the air. The residual fluorine concentration can be measured with high accuracy, and the silicon oxide concentration in phosphoric acid can be estimated with high accuracy from the measured value of fluorine concentration. Further, the phosphoric acid solution regenerating apparatus 6 can suppress phosphoric acid as a waste solution as much as possible, and can suppress not only cost reduction but also adverse effects on the environment.

  The present invention is not limited to the above embodiments, and various modifications and developments are possible within the scope of the gist of the present invention. For example, the following aspects can be taken. FIG. 3 shows an example of a modification.

  In order to perform the etching process under appropriate conditions, when a part of phosphoric acid is discharged from the circulation filtration path part 5, the entire amount of phosphoric acid overflowed when the wafer cassette 2 is put into the etching tank 3 is directly collected in the receiving tank 70. can do. In this case, when the wafer cassette 2 is put into the etching tank 3, the control circuit 300 opens the automatic valve 65 of the branch pipe 62. Thereby, the phosphoric acid overflowing the overflow part 3a is directly collected in the receiving tank 70 via the branch pipe 62, and a part of the phosphoric acid having a high silicon oxide concentration can be reliably discharged.

  The regenerated phosphoric acid in the storage tank 130 may be supplied not to the overflow part 3 a but to the circulation filtration path part 5 or to the main body of the etching tank 3. This case will be described with reference to FIG. When supplying to the circulation filtration path part 5, as shown in FIG. 3, the branch supply piping 160 can be provided in the supply piping 140a. The branch replenishment pipe 160 can be connected to the upstream side of the filter 51 of the circulation filtration path unit 5 and has an automatic valve 161. When the automatic valve 161 is opened, the regenerated phosphoric acid is supplied to the front of the filtration unit (filter 51) of the circulation filtration path unit 5 via the branch supply pipe 160. With such a structure, the supplied phosphoric acid passes through the filter 51, the line heater 52, and the like of the circulation filtration path 5, and the temperature and concentration are adjusted while being supplied from the supply port 35 to the etching tank 3. Is done. Further, since it passes through the filter 51, there is an advantage that such particles can be removed when the regenerated phosphoric acid contains particles.

  When the capacity of the etching tank 3 is large, etc., the processing tanks 100 may be provided in pairs, and the recovered phosphoric acid in the receiving tank 70 may be introduced into both the processing tanks 100 by a switching method and regenerated.

  A flow meter is provided in the discharge pipe 60 and the branch pipe 62 to measure the amount of recovered phosphoric acid, and based on the amount, regenerated phosphoric acid or new phosphoric acid can be supplied to the etching tank 3.

  The pure water supplied to the circulation filtration path unit 5 and the treatment tank 100 can actually be sent from the same pure water reservoir through the illustrated pipes.

  As a structure for discharging phosphoric acid from the etching tank 3, an embodiment in which the bottom wall 31 is not provided with the discharge port 36 will be described with reference to FIG. As shown in FIG. 3, a discharge pump 170 can be provided in the branch pipe 62. In this case, it is not necessary to provide the discharge port 36 in the bottom wall 31 of the etching tank 3. When discharging the phosphoric acid from the etching tank 3, when the discharge pump 170 provided in the branch pipe 62 is operated, first, the phosphoric acid in the circulation filtration path portion 5 flows back through the branch pipe 62. 70 is recovered. Furthermore, phosphoric acid in the etching tank 3 is discharged from the supply port 35, flows backward through the circulation filtration path portion 5, and is collected in the receiving tank 70 via the branch pipe 62. In this way, phosphoric acid in the etching tank 3 can be discharged.

  When the discharge pump is not used, since the liquid is collected by the gravity drop method, there is a problem that it takes time to collect the liquid and there is a restriction on the arrangement of the apparatus. As described above, by providing the discharge pump 170, the liquid recovery time can be shortened, and restrictions on the arrangement of the apparatus are reduced. Further, in this case, the supply port 35 of the bottom wall 31 of the etching tank 3 functions as a supply port when supplying the phosphoric acid in the circulation filtration path 5 and as a discharge port when discharging the phosphoric acid in the etching tank 3. Can be fulfilled.

  Further, for example, as shown in FIGS. 1 and 2, even if the discharge port 36 is provided and the discharge port 36 and the receiving tank 70 are connected by the discharge pipe 60, a discharge pump is connected to the discharge pipe 60. By providing, the liquid recovery time can be shortened, and the restriction on the arrangement of the apparatus can be reduced.

  In addition to being provided in the branch pipe 62, this discharge pump is used when injecting phosphoric acid such as a pipe connecting the receiving tank 70 and the processing tank 100 and a pipe connecting the processing tank 100 and the storage tank 130. Can be used for piping.

  As described above, in the wafer processing apparatus of the present invention, the total time for exchanging phosphoric acid in the etching bath 3 can be shortened, so that the stop time of the apparatus can be shortened. Further, new phosphoric acid is supplied as necessary, the liquid level of phosphoric acid in the etching tank 3 can be kept constant, and a stable etching process can be performed.

It is a block diagram which made the main part the etching part and circulation filtration path part of the processing apparatus concerning this Embodiment. It is a block diagram which made the phosphoric acid reproduction | regeneration part of the processing apparatus concerning this Embodiment a main body. It is a block diagram which made the main part the etching part and circulation filtration path | route part of the processing apparatus concerning the modification of this Embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Semiconductor wafer (wafer), 3 Etching tank, 3a Overflow part, 4 Etching part, 5 Circulation filtration path part, 6 Phosphate regenerator, 7 Measuring part, 8 New liquid supply part, 51 Filter (filtration part), 60 Discharge Piping, 62 branch piping, 70 receiving tank, 100 treatment tank, 109 hydrofluoric acid tank (HF tank), 116 filtration piping, 119 filter (filtering part), 130 storage tank, 140a replenishment piping, 140b circulation piping, 150 branch piping, 200 cooler, 201 constant temperature bath (including spiral tube), 203 heat insulation container, 204 conductivity sensor, 205 conductivity meter (fluorine meter), 300 control circuit (control means)

Claims (24)

An etching portion including an etching tank for etching a semiconductor wafer with phosphoric acid;
A branch pipe connected to the etching section;
A filtration unit connected to the branch pipe;
A first pipe for introducing the phosphoric acid that has passed through the filtration unit into the etching unit;
A phosphoric acid regenerator connected to the branch pipe;
A treatment tank provided in the phosphoric acid regenerating apparatus;
A cooler, a thermostat, and a measurement unit provided in the processing tank;
A processing apparatus comprising: means for controlling the phosphoric acid in the etching tank to be exchanged based on the number of etchings performed in the etching tank. The processing apparatus according to claim 1, wherein
The processing apparatus, wherein the etching part further includes an overflow part provided around the etching tank. The processing apparatus according to claim 1 or 2,
The etching unit has a supply port on the bottom wall of the etching unit,
The first piping is connected to the supply port. The processing apparatus according to any one of claims 1 to 3,
The branch pipe has a first valve;
If the hydraulic pressure is equal to or higher than a predetermined value, the processing apparatus is characterized in that the first valve is controlled to be in an open state. The processing apparatus according to any one of claims 1 to 4,
The branch pipe includes a first flow meter,
A processing apparatus, comprising: means for controlling the phosphoric acid to be introduced from the phosphoric acid regenerating apparatus into the etching portion based on the amount of phosphoric acid measured by the first flow meter. In the processing apparatus in any one of Claims 1 thru | or 5,
The processing apparatus according to claim 1, wherein the first branch pipe has means for controlling a flow rate of the phosphoric acid introduced into the phosphoric acid regenerating apparatus in accordance with a liquid pressure of the phosphoric acid flowing to the filtration unit. The processing apparatus according to any one of claims 1 to 6,
The processing apparatus, wherein the fluid pressure is measured using a pressure gauge. The processing apparatus according to any one of claims 1 to 7,
Means for heating the phosphoric acid connected to the filtration unit and introduced from the filtration unit;
A first pure water adding means provided between the means for heating the phosphoric acid and the etching portion, wherein the phosphoric acid heated by the means for heating is introduced. Processing equipment. The processing apparatus according to any one of claims 1 to 8,
The phosphoric acid regeneration device includes a receiving tank provided between the first branch pipe and the processing tank,
And a storage tank into which the phosphoric acid is introduced from the processing tank. The processing apparatus according to claim 9, wherein
The etching part further has a discharge port,
The processing apparatus characterized by including the 2nd piping which connects the said discharge port and the said receiving layer. The processing apparatus according to claim 10, wherein
The second pipe further includes a second flow meter,
A processing apparatus comprising: means for controlling the phosphoric acid to be introduced into the etching portion from the phosphoric acid regenerating apparatus based on the amount of phosphoric acid measured by the second flow meter. The processing apparatus according to claim 10 or 11,
The processing apparatus according to claim 2, wherein the second pipe includes a first pump. The processing apparatus according to any one of claims 1 to 9 or 12,
The branch pipe further includes a second pump. The processing apparatus according to any one of claims 9 to 13,
The treatment tanks are provided in pairs,
The said phosphoric acid introduce | transduced from the said receiving tank is introduced into the said processing tank provided in the pair by the switching system, The processing apparatus characterized by the above-mentioned. The processing apparatus according to any one of claims 1 to 14,
The processing unit, wherein the measurement unit includes a conductivity meter. The processing apparatus according to any one of claims 9 to 15,
A first path for introducing the phosphoric acid from the treatment tank to the storage tank;
And a second path for filtering and heating the phosphoric acid and reintroducing it into the processing tank. The processing apparatus according to any one of claims 9 to 16,
The processing apparatus, wherein the storage tank includes means for controlling the temperature of the phosphoric acid. The processing apparatus according to any one of claims 9 to 17,
The storage tank further includes a second pure water addition unit. The processing apparatus according to any one of claims 9 to 18,
A third path for introducing the phosphoric acid from the reservoir to the etched portion;
And a fourth path for reintroducing the phosphoric acid introduced into the third path into the storage tank. The processing apparatus according to claim 19, wherein
The processing apparatus further comprising a fifth path for introducing the phosphoric acid from the third path to the filtration unit. The processing apparatus according to claim 19 or 20,
The processing apparatus further comprising a new medicine supply unit connected to the third path. The processing apparatus according to any one of claims 1 to 21,
The processing apparatus according to claim 1, wherein the exchange of the phosphoric acid is a total amount. In the processing apparatus in any one of Claims 1 thru | or 22,
The processing apparatus is characterized in that the number of etchings is performed by measuring the loading / unloading of a wafer cassette into / from the etching unit.   24. A method for manufacturing a semiconductor device, wherein the semiconductor device is manufactured using the processing apparatus according to claim 1.

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