JP2011166064A - Method of manufacturing semiconductor device, and device for manufacturing semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To rapidly and effectively etch a processing object film containing a noble metal or the like using a diluted solution, and to improve an operation ratio of a facility. <P>SOLUTION: In this method of manufacturing a semiconductor device using this device for manufacturing a semiconductor device including a chemical preparation tank 24 for preparing a chemical, a chemical storage tank 28 for storing the prepared chemical, and a processing chamber 21 for processing a semiconductor substrate using the stored chemical, a first chemical is prepared by mixing an oxidizer with a complexing agent in the chemical preparation bath 24, and the first chemical is activated in the chemical preparation tank 24. Successively, the activated first chemical is mixed with pure water in the chemical storage tank 28, and the concentration and temperature of the first chemical are adjusted, whereby a second chemical obtained by diluting the first chemical is prepared. Successively, the second chemical is supplied to a semiconductor substrate inputted to the processing chamber 21. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a semiconductor device manufacturing method and a semiconductor device manufacturing apparatus using the same, and more particularly, to a semiconductor device manufacturing method for processing a film to be processed containing a noble metal using a dilute aqueous solution, and a semiconductor device manufacturing using the same. Relates to the device.

  In a CMOS (Complementary Metal-Oxide-Semiconductor) micro process, there is a demand for higher performance and lower power consumption of semiconductor devices. Under such circumstances, in the conventional CMOS process, in order to further reduce the resistance of silicide, which is an alloy of the first generation silicide metal material such as tungsten (W) and silicon, the second generation silicide metal is used. As a material, nickel silicide (NiSi) or cobalt silicide (CoSi) using nickel (Ni) or cobalt (Co) has been used.

  On the other hand, however, in the fine process, it is necessary to control the silicide reaction of NiSi and CoSi in order to reduce the junction leakage current. For this reason, an alloy in which about 5% to 10% platinum (Pt) or palladium (Pd) is mixed with Ni or Co is used as a silicide material. In particular, when an alloy of Ni and Pt (NiPt) is used as a silicide material, an effect of improving heat resistance and suppressing junction leakage current is expected.

In the silicidation step, the alloy is formed on a semiconductor substrate made of silicon (Si) and then subjected to a predetermined heat treatment, whereby the alloy and Si react to form metal silicide. At this time, it is necessary to remove the remaining unreacted alloy. Therefore, for example, when an alloy of Ni and Pt (NiPt) is used as a silicide material, sulfuric acid (H ₂ SO ₄ ) and hydrogen peroxide (H ₂ O) are used to remove unreacted NiPt after the formation of the silicide. _An acid having a high oxidizing power such as a mixed solution with ₂ ) is used (see, for example, Patent Document 1).

  Hereinafter, a silicide formation step in the conventional method for manufacturing a semiconductor device will be described with reference to FIGS. 9 (a) and 9 (b).

  First, in the step shown in FIG. 9A, a semiconductor substrate 101 made of Si is prepared. Thereafter, an insulating film 102 having an opening pattern is selectively formed in a silicide formation region on the semiconductor substrate 101. Subsequently, a NiPt film 103 that is a silicide material is formed on the entire surface of the semiconductor substrate 101 including the insulating film 102. Thereafter, by performing a predetermined heat treatment, a silicide layer 104 made of a mixed crystal of NiSi and NiPtSi is formed in the silicide formation region on the upper portion of the semiconductor substrate 101. In the following description, mixed crystals of NiSi and NiPtSi are collectively referred to as NiPtSi.

  Next, in the step shown in FIG. 9B, the unreacted NiPt film 103 remaining on the top and side surfaces of the insulating film 102 is removed using a mixed solution 105 of sulfuric acid and hydrogen peroxide. As a result, NiPtSi formed on the upper portion of the semiconductor substrate 101 remains. In this way, when removing the unreacted NiPt film 103 in the silicide formation process, Ni can be dissolved even if an acid having a high oxidizing power such as the mixed solution 105 of sulfuric acid and hydrogen peroxide is used. Although it can, Pt with low chemical reactivity cannot be dissolved. Therefore, Pt remains on the semiconductor substrate 101. For this reason, in order to prevent Pt from remaining, instead of the mixed solution 105 of sulfuric acid and hydrogen peroxide, dilute aqua regia (a solution containing nitric acid, hydrochloric acid and water) having a stronger oxidizing power is used. (For example, see Patent Document 2).

JP 2002-124487 A JP 2009-056347 A JP 2009-535846 A

  However, it has been confirmed that the following problems occur when attempting to dissolve a residual film containing Pt, a Pt contaminant or a Pt film using dilute aqua regia.

  In dilute aqua, nitrosyl chloride (NOCl) is produced by the reaction of hydrochloric acid and nitric acid, and Pt is dissolved as a chloride by the oxidizing power of the produced nitrosyl chloride.

  However, as shown in FIG. 10A, the etching amount of Pt is unstable unless about 2 hours elapse after the nitrosyl chloride is generated and the concentration thereof is stabilized.

  As shown in FIG. 10 (b), when cleaning by etching using such an unstable diluted water, the predetermined Pt etching amount (for example, Pt etching amount> 20 nm) is not reached. Many Pt residues (in circles) are generated due to insufficient cleaning.

  In addition, when trying to stabilize the Pt etching rate, which is a cleaning performance, it is necessary to pass at least 2 hours after the chemical solution is prepared. During that time, the cleaning apparatus cannot perform the chemical solution treatment and must wait. There is also a problem that the operating rate of the equipment is greatly reduced.

  That is, each time the chemical solution is changed, the time for introducing nitric acid, hydrochloric acid and water into the chemical solution preparation tank, the aging time of about 2 hours for stabilizing the cleaning performance, and the semiconductor substrate etc. with a high temperature chemical solution In the case of processing, it takes time to raise the temperature of the chemical solution by heating, and the equipment operation rate is significantly reduced.

  The present invention has been made in view of the above-described problems, and it is an object of the present invention to be able to quickly and effectively etch a film to be processed containing a noble metal using a diluted solution and improve the operating rate of equipment. And

  In order to achieve the above-mentioned object, a semiconductor device manufacturing method is prepared by previously activating a mixture of an oxidizing agent and a complexing agent in a preparation tank by an activating means, and diluting the activated mixture with pure water in a storage tank. Thus, the chemical solution is adjusted, and the semiconductor substrate is processed using the adjusted chemical solution.

  Specifically, the method for manufacturing a semiconductor device according to the present invention includes a chemical solution preparation tank for preparing a chemical solution, a chemical solution storage tank for storing the prepared chemical solution, and a processing chamber for processing a semiconductor substrate using the stored chemical solution. (A) for preparing a first chemical solution by mixing an oxidizing agent and a complexing agent in a chemical solution preparation tank, and a chemical solution for a semiconductor device manufacturing method using a semiconductor device manufacturing apparatus comprising: In the preparation tank, the step (b) of activating the first chemical liquid, and the activated first chemical liquid and pure water are mixed in the chemical liquid storage tank to adjust the concentration and temperature of the first chemical liquid. Thus, the method includes a step (c) of adjusting the second chemical solution obtained by diluting the first chemical solution, and a step (d) of supplying the second chemical solution to the semiconductor substrate placed in the processing chamber.

  According to the method for manufacturing a semiconductor device of the present invention, in the chemical liquid preparation tank, the first chemical liquid is prepared by mixing the oxidizing agent and the complexing agent, and the first chemical liquid is activated in the chemical liquid preparation tank. After that, in the chemical solution storage tank, the activated first chemical solution and pure water are mixed, and the concentration and temperature of the first chemical solution are adjusted to adjust the second chemical solution diluted with the first chemical solution. To do. For this reason, since the 2nd chemical | medical solution stored in a chemical | medical solution storage tank and supplied to a semiconductor substrate is fully activated in the chemical | medical solution preparation tank beforehand, when processing a semiconductor substrate, in a 2nd chemical | medical solution The reactivity is high enough. Therefore, it is possible to quickly and effectively etch a film to be processed containing a noble metal, and to improve the operating rate of equipment.

  In the method for manufacturing a semiconductor device of the present invention, in step (c), after supplying pure water to the chemical solution storage tank, the activated first chemical solution may be supplied to the chemical solution storage tank.

  In the method for manufacturing a semiconductor device of the present invention, the step (b) preferably includes a step (b1) of heating the first chemical solution.

  In this case, in the step (b1), the first chemical solution may be heated for a time of 5 minutes to 15 minutes and a temperature of 70 ° C. to 90 ° C.

  In the method for manufacturing a semiconductor device of the present invention, the step (b) preferably includes a step (b2) of irradiating the first chemical liquid with UV light.

In this case, in the step (b2), UV light, the wavelength is 100nm or more and 400nm or less, pulse energy - is at 0.1 J / cm ² or more and 10J / cm ² or less, and a UV light or 1 minute You may irradiate in 15 minutes or less.

  In the method for manufacturing a semiconductor device of the present invention, the step (b) may include a step (b3) of heating the first chemical solution and irradiating the first chemical solution with UV light.

In this case, in the step (b3), the first chemical solution is heated at a temperature of 70 ° C. or more and 90 ° C. or less, the wavelength is 100 nm or more and 400 nm or less, and the pulse energy is 0.1 J / cm. UV light is ² or more and 10J / cm ² or less may be irradiated with 30 seconds or more and 10 minutes or less.

In the method for manufacturing a semiconductor device of the present invention, the irradiated UV light may include F ₂ light, ArF light, KrCl light, KrF light, XeCl light, or XeF light.

  In the method for manufacturing a semiconductor device of the present invention, the step (b) may include a step (b4) of measuring the absorbance of the first chemical solution.

  In the method of manufacturing a semiconductor device of the present invention, in the step (c), the activated first chemical liquid and pure water are mixed to adjust the second chemical liquid to a desired temperature and a desired concentration. Also good.

  In the method for manufacturing a semiconductor device of the present invention, the oxidizing agent is at least one selected from the group consisting of nitric acid, hydrogen peroxide, ozone water, sulfuric acid, electrolytic sulfuric acid water, potassium permanganate, chromium trioxide, and osmium tetroxide. It may contain one.

  In the method for producing a semiconductor device of the present invention, the complexing agent is hydrochloric acid, calcium chloride, potassium chloride, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, hydroiodic acid. And at least one selected from the group consisting of sodium iodide, potassium iodide, calcium iodide, hydrobromic acid, sodium bromide, potassium bromide and calcium bromide.

  In the method for manufacturing a semiconductor device of the present invention, in the step (d), the second chemical solution may be supplied to the semiconductor substrate at a temperature of 23 ° C. or more and 60 ° C. or less.

 In the method for manufacturing a semiconductor device of the present invention, in the step (a), the second chemical solution is adjusted using a nitric acid aqueous solution having a nitric acid concentration of 70%, a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 36%, and pure water. The hydrochloric acid aqueous solution and the pure water may have a volume ratio of 1 to 5, and the hydrochloric acid aqueous solution may be 1 to 5 and the pure water may be 3 to 500.

  The apparatus for manufacturing a semiconductor device according to the present invention mixes a chemical solution preparation tank for preparing a first chemical solution by mixing an oxidizing agent and a complexing agent, and a first chemical solution prepared in the chemical solution preparation tank is mixed with pure water. Then, the second chemical solution obtained by diluting the first chemical solution is adjusted, the chemical solution storage tank for storing the adjusted second chemical solution, and the second chemical solution stored in the chemical solution storage tank are contained in the semiconductor. A treatment chamber for supplying to the substrate, and the chemical preparation tank has an activating means for activating the first chemical.

  According to the semiconductor device manufacturing apparatus of the present invention, the chemical liquid preparation tank for adjusting the first chemical liquid by mixing the oxidizing agent and the complexing agent has the activating means for activating the first chemical liquid. . For this reason, the 1st chemical | medical solution adjusted in the chemical | medical solution preparation tank is obtained by mixing with pure water, and the diluted 2nd chemical | medical solution supplied to a semiconductor substrate is fully activated in the chemical | medical solution preparation tank beforehand. Therefore, when the semiconductor substrate is etched or cleaned, the reactivity in the second chemical solution is sufficiently high. Therefore, it is possible to quickly and effectively etch a film to be processed containing a noble metal, and to improve the operating rate of equipment.

  In the semiconductor device manufacturing apparatus of the present invention, the activating means may be a heating mechanism.

  In this case, the heating mechanism may heat the first chemical solution for a time of 5 minutes or more and 15 minutes or less and at a temperature of 70 ° C. or more and 90 ° C. or less.

  In the semiconductor device manufacturing apparatus of the present invention, the activating means may be a UV light irradiation mechanism.

In this case, the UV light irradiation mechanism applies UV light having a wavelength of 100 nm to 400 nm to the first chemical solution at a repetition frequency of 5 Hz to 600 kHz, an output of 2 W to 800 W, and 0.1 J / Irradiation may be performed at a pulse energy of cm ² or more and 10 J / cm ² or less for a time of 1 minute or more and 15 minutes or less.

  In the semiconductor device manufacturing apparatus of the present invention, the activating means may be a heating mechanism and a UV light irradiation mechanism.

In this case, the heating mechanism heats the first chemical solution at a temperature of 70 ° C. or more and 90 ° C. or less, and the UV light irradiation mechanism applies UV light having a wavelength of 100 nm or more and 400 nm or less to the first chemical solution. and 600kHz or less of the repetition frequency above 5 Hz, 2W or more and 800W output below, and 0.1 J / cm ² or more and 10J / cm ² or less pulse energy - a, and irradiated with 30 seconds or more and 10 minutes or less May be.

  According to the semiconductor device manufacturing method and the semiconductor device manufacturing apparatus using the semiconductor device according to the present invention, it is possible to quickly and effectively etch a film to be processed and the like containing a noble metal using a diluted solution. The operating rate can be improved.

(A)-(d) is the manufacturing method of the semiconductor device which concerns on the 1st Embodiment of this invention, Comprising: It is sectional drawing of the order of a process which shows the silicide formation process using the aqua regia adjusted by this invention. is there. 1 is a schematic configuration diagram illustrating a semiconductor device manufacturing apparatus according to a first embodiment of the present invention. It is a washing | cleaning flowchart which shows the manufacturing method of the semiconductor device which concerns on the 1st Embodiment of this invention. It is a graph which shows the elapsed time dependence after the chemical | medical solution preparation of the Pt etching amount using the dilute aqua regia which concerns on the 1st Embodiment of this invention. It is a schematic block diagram which shows the manufacturing apparatus of the semiconductor device which concerns on the 2nd Embodiment of this invention. It is a washing | cleaning flowchart which shows the manufacturing method of the semiconductor device which concerns on the 2nd Embodiment of this invention. It is a graph which shows the elapsed time dependence after the chemical | medical solution preparation of the Pt etching amount using the dilute aqua regia which concerns on the 2nd Embodiment of this invention. It is a schematic block diagram which shows the manufacturing apparatus of the semiconductor device which concerns on the modification of the 2nd Embodiment of this invention. It is typical sectional drawing of the order of a process which shows the conventional silicide formation method. (A) is a graph which shows the elapsed time dependence after the chemical | medical solution preparation of the Pt etching amount using the conventional rare aqua regia. (B) is an electron micrograph showing the Pt residue after etching using conventional dilute aqua regia.

(First embodiment)
A method and apparatus for manufacturing a semiconductor device according to a first embodiment of the present invention will be described with reference to the drawings.

  FIG. 1A to FIG. 1D show a manufacturing method until forming NiPt silicide for a MOS transistor having a gate structure using the dilute aqua regia adjusted in the first embodiment in order of steps. ing.

First, as shown in FIG. 1A, for example, an element isolation region 12 is selectively formed on a semiconductor substrate 11 made of silicon (Si) by STI (shallow trench isolation) or the like. Thereafter, a gate insulating film 13 made of, for example, silicon oxide (SiO ₂ ) is formed on the semiconductor substrate 11 surrounded by the element isolation region 12, and a gate electrode (conductive film made of polycrystalline silicon is formed on the gate insulating film 13. ) 14 are sequentially formed. Subsequently, sidewalls 15 made of silicon oxide are formed on both side surfaces of the gate electrode 14 by a known method. Thereafter, source / drain diffusion layers 19 containing high-concentration impurities are selectively formed in regions on both sides of the gate electrode 14 in the semiconductor substrate 11 to obtain a MOS transistor.

  Next, as shown in FIG. 1B, a mask made of silicon oxide having a thickness of about 20 nm to 70 nm and having no impurities introduced over the entire surface of the semiconductor substrate 11 including the gate electrode 14 and the sidewall 15. A film 16 is formed. Subsequently, the upper portion of the silicide formation region in the mask film 16 is selectively removed to expose the upper surface of the gate electrode 14 and the upper surface of the source / drain diffusion layer 19. Thereafter, a NiPt film 17 having a Pt content of 2 wt% or more and 10 wt% or less and a film thickness of 7 nm or more and 25 nm or less is formed on the entire surface of the semiconductor substrate 11 by sputtering or the like. .

  Next, as shown in FIG. 1C, heat treatment is performed at a temperature of about 200 ° C. or more and 400 ° C. or less to form the source / drain diffusion layer 19 and the gate electrode 14 in the semiconductor substrate 11. The NiPt film 17 is reacted with the silicon of the semiconductor substrate 11 and the polycrystalline silicon of the gate electrode 14, respectively. Thereby, a silicide layer 18 made of NiPtSi having a film thickness of about 8.5 nm or more and 25.5 nm or less is formed on the upper surface of the gate electrode 14 and the upper surface of the source / drain diffusion layer 19, respectively. At this time, the NiPt film 17 on the mask film 16 and the side surface of the sidewall 14 does not undergo a silicide reaction and remains as it is.

  Next, as shown in FIG. 1D, the NiPt film 17 remaining without contributing to silicidation is removed using dilute aqua regia. Here, the temperature of the dilute water is, for example, not less than room temperature and not more than 70 ° C., and the concentration thereof is, for example, when the aqueous nitric acid solution is 1 by volume, the aqueous hydrochloric acid solution is not less than 1 and not more than 5 Pure water is about 3 to 500.

  Hereinafter, a method for removing the NiPt film 17 using the diluted aqua regia according to the first embodiment will be described with reference to FIGS.

  First, FIG. 2 shows a schematic configuration of a semiconductor device manufacturing apparatus according to the first embodiment.

  As shown in FIG. 2, the manufacturing apparatus 20 includes a processing chamber 21 that processes a semiconductor substrate (not shown) and the like with a diluted chemical, a chemical storage tank 28 that stores a chemical supplied to the processing chamber 21, For example, a chemical solution mixing tank 24 for mixing and activating a predetermined amount of nitric acid as an oxidizing agent and hydrochloric acid as a complexing agent is provided.

  The chemical preparation tank 24 is provided with a nitric acid supply source 22 for supplying nitric acid to the preparation liquid combination tank 24 via a supply pipe 25A, and a hydrochloric acid supply source 23 for supplying hydrochloric acid via a supply pipe 25B. Yes. The chemical liquid preparation tank 24 includes a first temperature adjustment mechanism (for example, a heater) 26A as a heating mechanism for activating the mixed chemical liquid of nitric acid and hydrochloric acid by heating, and a spectrophotometer for measuring the absorbance of the mixed chemical liquid. 29.

  The chemical solution storage tank 28 includes a pure water supply source 27 that supplies pure water at a desired temperature to the chemical solution storage tank 28 via a supply pipe 25C, and a mixture of nitric acid and hydrochloric acid activated in the chemical solution preparation tank 24. An introduction pipe 25D for introducing the chemical liquid from the chemical liquid preparation tank 24 and a second temperature adjustment mechanism (heater) 26B for adjusting the temperature of the mixed chemical liquid are provided.

  The processing chamber 21 has an introduction pipe 25E for introducing the mixed chemical liquid whose temperature is adjusted in the chemical liquid storage tank 28 from the chemical liquid storage tank 28, and an introduction pipe 25F for circulating the mixed chemical liquid processed in the processing chamber 21 to the chemical liquid storage tank 28. And a waste liquid pipe 25G connected to the waste liquid line.

  Next, a manufacturing method using the manufacturing apparatus 20 according to the first embodiment will be described based on the flowchart shown in FIG.

  As shown in FIG. 3, the flow A shows the operation sequence of the chemical solution preparation tank 24, the flow B shows the operation sequence of the chemical solution storage tank 28, and the flow C shows the operation sequence of the processing chamber 21.

  First, in Step A1, a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid are introduced into the chemical liquid preparation tank 24 to adjust the mixed chemical liquid.

  Next, in step A2, the mixed chemical liquid adjusted in the chemical liquid preparation tank 24 is heated and activated by the first temperature adjustment mechanism 26A. At this time, the first temperature adjustment mechanism 26A is preferably heated at a temperature of about 70 ° C. to 90 ° C. for about 5 minutes to 15 minutes.

  At this time, in step B1, a predetermined amount of pure water at a desired temperature is charged into the chemical solution storage tank 28 until the mixed chemical solution in the chemical preparation tank 24 is activated. To do. Here, the temperature of pure water is preferably, for example, from room temperature to about 40 ° C.

  Next, in step A3 and step B2, an activated mixed chemical solution of nitric acid and hydrochloric acid is introduced from the chemical preparation tank 24 into the chemical storage tank 28 into which pure water has been charged in advance, and adjusted to a desired chemical concentration. .

  Next, in step B3, the mixed chemical introduced into the chemical storage tank 28 is adjusted to a desired temperature using the second temperature adjustment mechanism 26B. Here, the second temperature adjustment mechanism 26B can be adjusted to a temperature of 20 ° C. or more and 80 ° C. or less. Further, the temperature of the chemical solution supplied to the processing chamber 21 is preferably about 23 ° C. or more and 60 ° C. or less.

  Next, in step C <b> 1, the temperature adjustment of the chemical solution in the chemical solution storage tank 28 is completed, and at the same time, the semiconductor substrate is carried into the processing chamber 21.

  Next, in step B4 and step C2, a chemical solution adjusted to a desired concentration and temperature in the chemical solution storage tank 28 is introduced into the processing chamber 21, and a predetermined process such as an etching process or a cleaning process is performed on the semiconductor substrate. Do.

  Next, in step C3, the treated semiconductor substrate is washed (rinsed) and then dried.

  Next, in step C4, the semiconductor substrate that has been subjected to the drying process is unloaded from the processing chamber 21.

  As described above, according to the method for manufacturing a semiconductor device using the manufacturing apparatus 20 according to the first embodiment, a mixed chemical solution containing a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid charged into the chemical liquid preparation tank 24 is prepared. When heating at 70 ° C. or more and 90 ° C. or less for about 5 minutes or more and 15 minutes or less, the reaction between nitric acid and hydrochloric acid is activated and the reaction rate is improved. Therefore, when the activated mixed chemical solution is diluted with pure water in the chemical solution storage tank 28, the stored diluted chemical solution is immediately stored and immediately after the temperature is adjusted, the stable dissolution performance with respect to platinum (Pt). Therefore, substrate processing can be performed efficiently.

  That is, in the conventional chemical liquid adjustment method in which nitric acid and hydrochloric acid are reacted at room temperature, it is necessary to wait for the manufacturing apparatus (processing apparatus) for about 2 hours from the time when the chemical liquid is prepared in order to stabilize the Pt etch rate. Conventionally, since the chemical solution is directly charged into the chemical solution storage tank in the manufacturing apparatus, the chemical solution cannot be heated to a high temperature.

  However, in the first embodiment, the chemical solution aging time until the Pt etch rate is stabilized can be shortened to 15 minutes or less. Furthermore, since the mixed chemical solution of nitric acid and hydrochloric acid is introduced into the chemical solution storage tank 28 into which pure water has been added in advance, the concentration of the chemical solution in the chemical solution storage tank 28 can be lowered. For this reason, the progress of the corrosion of the constituent members of the manufacturing apparatus 20 and the piping can be suppressed.

  Therefore, in this embodiment, the process with respect to a semiconductor substrate can be performed rapidly and effectively, and the operating rate of the manufacturing apparatus 20 can be improved. In addition, the progress of corrosion of the constituent members and piping of the manufacturing apparatus 20 can be suppressed.

  FIG. 4 shows the dependence of the Pt etching amount of dilute water on the elapsed time after the preparation of the chemical solution in the first embodiment and the conventional preparation method. Here, using a single wafer type apparatus, a Pt blanket film having a film thickness of 50 nm is treated with dilute aqua regia having a concentration of nitric acid: hydrochloric acid: pure water = 1: 5: 4 and a temperature of 60 ° C. for 2 minutes. It is carried out. Here, the conventional dilute water is prepared by mixing nitric acid, hydrochloric acid and pure water at room temperature, while the dilute water according to the first embodiment is prepared by mixing a mixed chemical solution of nitric acid and hydrochloric acid at 80 ° C. in the chemical preparation tank 24. The heat treatment is performed for 10 minutes.

  As shown in FIG. 4, in the conventional method for preparing dilute water in which nitric acid and hydrochloric acid are reacted at room temperature and then water is added, the etching amount of Pt is not stable until 2 hours after the dilute water is prepared. The amount of Pt etching is stabilized after 2 hours. On the other hand, in the first embodiment, it can be seen that the Pt etching amount is stable immediately after the preparation of dilute water (immediately after the heat treatment).

  As described above, according to the first embodiment, the chemical solution aging time until the amount of Pt etching is stabilized can be shortened from about 2 hours to 15 minutes or less, so the operating rate of the manufacturing apparatus 20 is large. improves.

  Below, the Pt dissolution reaction of dilute water will be described using chemical formulas (1) and (2).

  Diluted aqua regia reacts with hydrochloric acid and nitric acid to generate nitrosyl chloride as in formula (1), and dissolves Pt as chloride by the oxidizing power of nitrosyl chloride as in formula (2).

HNO ₃ + 3HCl → NOCl (nitrosyl chloride) + Cl ₂ + 2H ₂ O (1)
Pt + 2NOCl + Cl ₂ + 2HCl → H ₂ [PtCl ₆ ] + 2NO (2)
Here, as in the first embodiment, the mixed chemical solution of nitric acid and hydrochloric acid is heated at a temperature of about 70 ° C. to 90 ° C. for about 5 minutes to about 15 minutes, whereby the formula (1 ) And the reaction rate of nitric acid and hydrochloric acid is improved, and sufficient nitrosyl chloride is produced. For this reason, it is considered that the Pt etching rate is stabilized.

  Next, the chemical solution exchange of the chemical solution in the chemical solution storage tank 28 will be described using the flowchart of FIG. 3 again.

  As shown in FIG. 3, while the processing of the semiconductor substrate is being performed in the processing chamber 21, in step A4, a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid are mixed in the chemical liquid preparation tank 24 to mix the chemical solution. Formulate.

  Next, in Step A5, the mixed chemical solution is heated by the first temperature adjustment mechanism 26A to activate the mixed chemical solution.

  Next, after step B4, it is determined whether or not the chemical solution stored in the chemical solution storage tank 28 is to be replaced. If it is determined that the replacement is necessary, the mixed chemical solution in the chemical solution storage tank 28 is discarded in the next step B5.

  Next, in step B6, a predetermined amount of pure water is poured into the chemical solution storage tank 28 at a predetermined temperature (from room temperature to about 40 ° C.).

  Next, in steps A6 and B7, an activated mixed chemical solution of nitric acid and hydrochloric acid is introduced into the chemical storage tank 28 into which pure water has been introduced to adjust the concentration to a desired chemical concentration.

  Next, in step B8, the chemical solution adjusted to a desired chemical solution concentration is adjusted to a desired chemical solution temperature (from about 23 ° C. to about 60 ° C.) by the second temperature adjustment mechanism 26B.

  The chemical solution exchange in the chemical solution storage tank 28 is thus completed.

  By such a chemical solution exchange flow, when the chemical solution is exchanged, since the activated mixed chemical solution is already prepared in the chemical solution preparation tank 24, the activated mixed chemical solution is supplied to the chemical solution storage tank 28 as a chemical preparation. The chemical liquid exchange is completed simply by introducing from the tank 24 and adjusting the liquid temperature. For this reason, since the continuous processing is possible when the manufacturing apparatus 20 is a single wafer type, the operating rate of the manufacturing apparatus 20 is improved.

  In the first embodiment, the operation of adding and mixing a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid to the chemical liquid preparation tank 24 and the operation of heating and activating by the first temperature adjustment mechanism 26A are as follows. , Can be set arbitrarily according to the time of chemical exchange.

  In the first embodiment, for example, when a semiconductor substrate is processed using a relatively high temperature chemical solution having a temperature of about 40 ° C. to 60 ° C., the temperature is 70 ° C. to 90 ° C. The mixed chemical liquid heated to a certain degree is introduced into a chemical liquid storage tank 28 into which a predetermined amount of pure water is charged at a desired temperature. For this reason, if an appropriate amount of pure water is stored in the chemical solution storage tank 28 at an appropriate temperature so as to obtain a desired concentration of the chemical solution, the diluted chemical solution is immediately added after the mixed chemical solution is introduced into the chemical solution storage tank 28. The desired temperature can be obtained. As a result, the temperature of the chemical stored in the chemical storage tank 28 can be adjusted efficiently in a shorter time. Therefore, the operating rate of the manufacturing apparatus 20 can be further improved by reducing the temperature adjustment time of the chemical solution.

  Further, as described above, the chemical liquid preparation tank 24 is provided with the spectrophotometer 29 that measures the absorbance of the wavelength of visible light with respect to the mixed chemical liquid after being activated by mixing nitric acid and hydrochloric acid. The spectrophotometer 29 can manage the chemical concentration and temperature, and can stably operate the manufacturing apparatus 20. For example, when measuring the absorbance of nitrosyl chloride (NOCl) in a mixed chemical solution of nitric acid and hydrochloric acid, the absorption light wavelength having a wavelength of 580 nm or more and 610 nm or less is controlled within the range of the absorbance of 0.1 or more and 2 or less. It is preferable.

(Second Embodiment)
A method and apparatus for manufacturing a semiconductor device according to a second embodiment of the present invention will be described with reference to FIGS.

  FIG. 5 shows a schematic configuration of a semiconductor device manufacturing apparatus according to the second embodiment. In FIG. 5, the same components as those shown in FIG.

  In the semiconductor device manufacturing apparatus 20A according to the second embodiment, instead of the first temperature adjustment mechanism 26A, the activation means provided in the chemical liquid preparation tank 24 for activating the mixed chemical liquid of the oxidizing agent and the complexing agent is replaced. An ultraviolet (UV) light irradiation mechanism (for example, a UV irradiator) 30 is used. Other constituent members are equivalent to the manufacturing apparatus 20 according to the first embodiment.

  Next, based on the flowchart shown in FIG. 6, a manufacturing method using the manufacturing apparatus 20A according to the second embodiment will be described.

  In FIG. 6, the flow A shows the operation sequence of the chemical solution preparation tank 24, the flow B shows the operation sequence of the chemical solution storage tank 28, and the flow C shows the operation sequence of the processing chamber 21.

  As shown in FIG. 6, first, in step A1, a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid are introduced into the chemical liquid preparation tank 24 to adjust the mixed chemical liquid.

Next, in step A <b> 2 a, the mixed chemical liquid adjusted in the chemical liquid preparation tank 24 is activated by irradiating predetermined UV light with the UV light irradiation mechanism 30. At this time, the UV light irradiation mechanism 30 has a UV light wavelength of about 100 nm to about 400 nm, a repetition frequency of about 5 Hz to about 600 kHz, an output of about 2 W to about 800 W, and a pulse energy of 0.1 J / extent cm ² or more and 10J / cm ² or less, it is preferable to irradiate with the degree or less and 15 minutes more than one minute.

  At this time, in step B1, a predetermined amount of pure water at a desired temperature is added to the chemical solution storage tank 28 until the mixed chemical solution in the chemical preparation tank 24 is activated. . Here, the temperature of pure water is preferably, for example, about room temperature to about 80 ° C.

  Next, in step A3 and step B2, an activated mixed chemical solution of nitric acid and hydrochloric acid is introduced from the chemical preparation tank 24 into the chemical storage tank 28 into which pure water has been charged in advance, and adjusted to a desired chemical concentration. .

  Next, in step B3, the mixed chemical introduced into the chemical storage tank 28 is adjusted to a desired temperature using the second temperature adjustment mechanism 26B. The temperature of the chemical solution adjusted here and supplied to the processing chamber 21 is preferably about 23 ° C. or more and 60 ° C. or less.

  Next, in step C <b> 1, the temperature adjustment of the chemical solution in the chemical solution storage tank 28 is completed, and at the same time, the semiconductor substrate is carried into the processing chamber 21.

  Next, in step B4 and step C2, a chemical solution adjusted to a desired concentration and temperature in the chemical solution storage tank 28 is introduced into the processing chamber 21, and a predetermined process such as an etching process or a cleaning process is performed on the semiconductor substrate. Do.

  Next, in step C3, the treated semiconductor substrate is washed (rinsed) and then dried.

  Next, in step C4, the semiconductor substrate that has been subjected to the drying process is unloaded from the processing chamber 21.

As described above, according to the method of manufacturing a semiconductor device using the manufacturing apparatus 20A according to the second embodiment, the mixed chemical solution containing the predetermined amount of nitric acid and the predetermined amount of hydrochloric acid charged into the chemical liquid preparation tank 24 is used. For example, UV light having a wavelength of about 157 nm to about 355 nm, a repetition frequency of about 5 Hz to about 600 kHz, an output of about 2 W to about 800 W, and a pulse energy of about 0.1 J / cm ^{2 to} about 10 J / cm ^When irradiated for about 1 minute or more and about 15 minutes or less at about ² or less, the reaction between nitric acid and hydrochloric acid is activated and the reaction rate is improved, and the semiconductor substrate is processed with stable Pt dissolution performance immediately after the activation treatment. Can be applied.

  In the second embodiment, the UV light from the UV light irradiation mechanism 30 is used as the means for activating the mixed chemical solution of nitric acid and hydrochloric acid prepared in the chemical preparation tank 24 until the Pt etch rate is stabilized. The chemical aging time can be reduced to 15 minutes or less. Furthermore, since the mixed chemical solution is introduced into the chemical solution storage tank 28 into which pure water has been added in advance, the concentration of the chemical solution in the chemical solution storage tank 28 can be lowered. For this reason, it is possible to suppress the progress of corrosion of the constituent members and piping of the manufacturing apparatus 20A.

  Therefore, also in the present embodiment, the processing on the semiconductor substrate can be performed quickly and effectively, and the operating rate of the manufacturing apparatus 20A can be improved. In addition, the progress of corrosion of the constituent members and piping of the manufacturing apparatus 20A can be suppressed.

In FIG. 7, the elapsed time dependence after the chemical | medical solution preparation by 2nd Embodiment and the conventional preparation method with respect to the Pt etching amount of dilute water is shown. Here, using a single wafer apparatus, a Pt blanket film having a thickness of 50 nm is treated with dilute aqua regia at a concentration of nitric acid: hydrochloric acid: water = 1: 5: 4 and a temperature of 60 ° C. for 2 minutes. Is going. Here, the conventional dilute water is prepared by mixing nitric acid, hydrochloric acid and pure water at room temperature, while the dilute water according to the second embodiment is used for the mixed chemical solution of nitric acid and hydrochloric acid in the chemical solution preparation tank 24. In addition, UV light having a repetition frequency of 30 kHz, an output of 10 W, and a wavelength of 266 nm is activated by being irradiated at room temperature for 10 minutes.

  As shown in FIG. 7, in the conventional method for preparing dilute water in which nitric acid and hydrochloric acid are reacted at room temperature and then charged with water, the etching amount of Pt is not stable until 2 hours after the preparation of dilute water. The amount of Pt etching is stabilized after 2 hours. On the other hand, in the second embodiment, it can be seen that the Pt etching amount is stable immediately after the preparation of dilute water (immediately after the heat treatment).

  As described above, according to the second embodiment, the chemical solution aging time until the amount of Pt etching is stabilized can be shortened from about 2 hours to 15 minutes or less, so the operating rate of the manufacturing apparatus 20A is large. improves.

  Next, the chemical solution exchange of the chemical solution in the chemical solution storage tank 28 will be described using the flowchart of FIG. 6 again.

  As shown in FIG. 6, while the semiconductor substrate is being processed in the processing chamber 21, in step A4, a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid are mixed in the chemical liquid preparation tank 24 to mix the chemical solution. Formulate.

  Next, in step A5a, the mixed chemical solution is irradiated with UV light by the UV light irradiation mechanism 30 to activate the mixed chemical solution.

  Next, after step B4, it is determined whether or not the chemical solution stored in the chemical solution storage tank 28 is to be replaced. If it is determined that the replacement is necessary, the mixed chemical solution in the chemical solution storage tank 28 is discarded in the next step B5.

  Next, in step B6, a predetermined amount of pure water is poured into the chemical solution storage tank 28 at a predetermined temperature (from room temperature to about 80 ° C.).

  Next, in steps A6 and B7, an activated mixed chemical solution of nitric acid and hydrochloric acid is introduced into the chemical storage tank 28 into which pure water has been introduced to adjust the concentration to a desired chemical concentration.

  Next, in step B8, the chemical solution adjusted to the desired chemical solution concentration is adjusted to the desired chemical solution temperature by the second temperature adjustment mechanism 26B.

  The chemical solution exchange in the chemical solution storage tank 28 is thus completed.

  By such a chemical solution exchange flow, when the chemical solution is exchanged, since the activated mixed chemical solution is already prepared in the chemical solution preparation tank 24, the activated mixed chemical solution is supplied to the chemical solution storage tank 28 as a chemical preparation. The chemical exchange is completed simply by introducing from the tank 24 and adjusting the temperature. For this reason, since the continuous processing is possible when the manufacturing apparatus 20A is a single wafer type, the operating rate of the manufacturing apparatus 20A is improved.

  In the second embodiment, an operation of adding and mixing a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid to the chemical preparation tank 24, and an operation of irradiating and activating UV light by the UV light irradiation mechanism 30 Can be arbitrarily set according to the timing of the chemical exchange.

  In the second embodiment, for example, when a semiconductor substrate is processed using a relatively high temperature chemical solution having a temperature of about 40 ° C. or more and 60 ° C. or less, the mixed chemical solution activated by UV light is used. Is introduced into the chemical solution storage tank 28 into which a predetermined amount of pure water has been introduced, if warm pure water having an appropriate temperature is previously introduced in accordance with a desired concentration, the diluted chemical solution is added immediately after the chemical solution is mixed. The desired temperature can be obtained. For example, here, it is preferable to add warm pure water of about 40 ° C. or more and 80 ° C. or less. As a result, the temperature of the chemical stored in the chemical storage tank 28 can be adjusted efficiently in a shorter time. Therefore, the operating rate of the manufacturing apparatus 20A can be improved by shortening the temperature adjustment time of the chemical solution.

  Similarly to the first embodiment, also in the second embodiment, after the nitric acid and hydrochloric acid are mixed and activated in the chemical preparation tank 24, the absorbance at the wavelength of visible light with respect to the mixed chemical is shown. A spectrophotometer 29 for measurement is provided. The spectrophotometer 29 can manage the chemical concentration and temperature, and can stably operate the manufacturing apparatus 20A. For example, when measuring the absorbance of nitrosyl chloride (NOCl) in a mixed chemical solution of nitric acid and hydrochloric acid, the absorption light wavelength having a wavelength of 580 nm or more and 610 nm or less is controlled within the range of the absorbance of 0.1 or more and 2 or less. It is preferable.

In the second embodiment, the mixed chemical solution is activated by irradiating UV light. However, the present invention is not limited to this. For example, instead of UV light, F ₂ light (wavelength: 157 nm), ArF light (wavelength: 193 nm), KrCl light (wavelength: 222 nm), KrF light (wavelength: 248 nm), XeCl light (wavelength: 308 nm) or XeF Similar effects can be obtained by selecting from excimer laser light such as light (wavelength: 351 nm).

  Moreover, in 2nd Embodiment, although the case where it divided | segmented into the chemical | medical solution preparation tank 24 and the chemical | medical solution storage tank 28 was demonstrated, it was put together into the chemical | medical solution preparation tank 24 and the chemical | medical solution storage tank 28 as a chemical | medical solution preparation storage tank. One tank can also be used. In this case, the chemical preparation tank is provided with a UV light irradiation mechanism 30 and a spectrophotometer 29. The chemical preparation tank is mixed with a predetermined amount of nitric acid and a predetermined amount of hydrochloric acid and activated by UV light irradiation. To do. Thereafter, a predetermined amount of pure water at a predetermined temperature is added to the chemical liquid preparation storage tank filled with the activated chemical liquid to adjust the chemical liquid temperature and the chemical liquid concentration. Even in this case, the same effect as that of the second embodiment can be obtained only by whether the chemical preparation tank is divided into the chemical preparation tank and the chemical storage tank or not.

(One Modification of Second Embodiment)
FIG. 8 shows a schematic configuration of a semiconductor device manufacturing apparatus according to a modification of the second embodiment.

  As shown in FIG. 8, the manufacturing apparatus 20 </ b> B according to this modification is characterized in that the chemical liquid preparation tank 24 is provided with a first temperature adjustment mechanism 26 </ b> A as an activation means in addition to the UV light irradiation mechanism 30. And

  The semiconductor device manufacturing method using the manufacturing apparatus 20B according to the present modification is a cleaning flow that combines the cleaning flow of FIG. 3 and the cleaning flow of FIG. 6 in the first embodiment.

However, in the chemical preparation tank 24, the liquid temperature of the mixed chemical solution of nitric acid and hydrochloric acid is about 70 ° C. or more and 90 ° C. or less, and the pulse energy of the UV light to be irradiated is 0.1 J / cm ² or more and 10 J / cm ^The irradiation time is set to about 30 seconds or more and 10 minutes or less.

  Note that the UV light wavelength, repetition frequency, and output setting values are the same as those in the second embodiment.

  Even if it does in this way, the rapid and effective chemical | medical solution process with respect to a semiconductor substrate and the improvement of the operation rate of the manufacturing apparatus 20B can be aimed at.

  In the first embodiment, the second embodiment, and modifications thereof, the concentration of nitric acid or hydrochloric acid in the chemical solution stored in the chemical solution storage tank 28 decreases as the elapsed time and the substrate processing increase. There is a case. In this case, the chemical solution storage tank 28 can be replenished with a desired amount of the mixed chemical solution activated from the chemical solution preparation tank 24 as needed. Thereby, the concentration of nitric acid and hydrochloric acid in the chemical solution storage tank 28 is stabilized and the chemical solution lifetime can be extended, so that the consumption of the chemical solution is reduced and the operating rate of the manufacturing apparatuses 20, 20A, 20B is increased. improves.

  Moreover, in each embodiment and one modification, the density | concentration of the chemical | medical solution stored in the chemical | medical solution storage tank 28 can be suitably set according to the kind of target object which should be processed. For example, hydrochloric acid as a complexing agent can be a commercially available hydrochloric acid stock solution (aqueous solution with a hydrochloric acid concentration of 36%), and nitric acid as an oxidizing agent can be a commercially available nitric acid stock solution (aqueous solution with a nitric acid concentration of 70%). Therefore, the final concentration of dilute water is determined according to the amount of these stock solutions and pure water. For example, the volume ratio of nitric acid, hydrochloric acid, and pure water is preferably 1 or more and 5 or less for the hydrochloric acid stock solution and 5 or more and 500 or less for the pure water when the nitric acid stock solution is 1.

  In addition, after adding pure water in the chemical solution storage tank 28 and further adding nitric acid and hydrochloric acid, dilute aqua regia having a uniform concentration can be adjusted by appropriately circulating the chemical solution. Moreover, each capacity | capacitance of the chemical | medical solution preparation tank 24 and the chemical | medical solution storage tank 28 can be suitably adjusted according to the scale etc. of the manufacturing line of a semiconductor device.

  In each embodiment and one modified example, after the chemical processing on the semiconductor substrate is completed, dilute aqua regia is taken into the chemical storage tank 28 through the introduction pipe 25F and stored again in the chemical storage tank 28. The That is, the dilute aqua regia can circulate between the chemical solution storage tank 28 and the processing chamber 21. Further, as described above, the dilute water can be discarded into the waste liquid line via the waste liquid pipe 25G.

  Moreover, the chemical | medical solution preparation tank 24 can suppress advancing of the corrosion of the manufacturing apparatuses 20, 20A, and 20B by installing 5 m or more in piping length from the chemical | medical solution storage tank 28 and the processing chamber 21, and installing as a separate body. Therefore, in each embodiment and one modification, the manufacturing apparatuses 20, 20 </ b> A, and 20 </ b> B are configured to include the chemical liquid preparation tank 24, the chemical liquid storage tank 28, and the processing chamber 21, but are not limited to this configuration. 20A and 20B include a chemical storage tank 28 and a processing chamber 21, and the chemical preparation tank 24 may be a separate manufacturing apparatus.

  Moreover, even when it is set as a batch type manufacturing apparatus, the same effect can be acquired only by changing the capacity | capacitance of each tank as a processing method. In the case of a batch type, it is preferable to provide a washing tank and a drying tank separately from the processing chamber 21.

  In each embodiment and one modification, dilute aqua regia, which is a mixed chemical solution of nitric acid as an oxidizing agent and hydrochloric acid as a complexing agent, is used, but is not limited thereto. For example, a chemical solution containing at least one selected from hydrogen peroxide, ozone water, sulfuric acid, electrolytic sulfuric acid water, potassium permanganate, chromium trioxide and osmium tetroxide as an oxidizing agent, and calcium chloride as a complexing agent , Potassium chloride, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, hydroiodic acid, sodium iodide, potassium iodide, calcium iodide, hydrobromic acid, odor The same effect as dilute aqua regia can be obtained even with a chemical mixture comprising at least one selected from sodium bromide, potassium bromide and calcium bromide and pure water.

  In each embodiment and one modification, the noble metal added to the silicide layer refers to gold (Au), silver (Ag), and white metal elements (Ru, Rh, Pd, Os, Ir, and Pt).

  A semiconductor device manufacturing method and a semiconductor device manufacturing apparatus using the semiconductor device manufacturing method according to the present invention can etch a film to be processed containing a noble metal quickly and effectively using a diluted solution, and can operate a facility. It is useful for a manufacturing method of a semiconductor device that performs etching or cleaning, a manufacturing apparatus of a semiconductor device using the same, and the like.

DESCRIPTION OF SYMBOLS 11 Semiconductor substrate 12 Element isolation region 13 Gate insulating film 14 Gate electrode 15 Side wall 16 Mask film 17 NiPt film 18 Silicide layer 19 Source / drain diffusion layer 20 Manufacturing apparatus 20A Manufacturing apparatus 20B Manufacturing apparatus 21 Processing chamber 22 Nitric acid supply source 23 Hydrochloric acid supply Source 24 Chemical solution preparation tank 25A Supply pipe 25B Supply pipe 25C Supply pipe 25D Introduction pipe 25E Introduction pipe 25F Introduction pipe 25G Waste liquid pipe 26A First temperature adjustment mechanism (heating mechanism)
26B Second temperature adjustment mechanism 27 Pure water supply source 28 Chemical solution storage tank 29 Spectrophotometer 30 UV light irradiation mechanism

Claims (22)

A semiconductor device using a semiconductor device manufacturing apparatus having a chemical solution preparation tank for preparing a chemical solution, a chemical solution storage tank for storing the prepared chemical solution, and a processing chamber for processing a semiconductor substrate using the stored chemical solution A manufacturing method of
A step (a) of mixing the oxidizing agent and the complexing agent to prepare the first chemical solution in the chemical solution preparation tank;
A step (b) of activating the first chemical liquid in the chemical liquid preparation tank;
In the chemical solution storage tank, the activated first chemical solution and pure water are mixed, and the concentration and temperature of the first chemical solution are adjusted to dilute the first chemical solution. Step (c) of adjusting
And (d) supplying the second chemical solution to the semiconductor substrate put into the processing chamber.   2. The semiconductor device according to claim 1, wherein in the step (c), after the pure water is supplied to the chemical solution storage tank, the activated first chemical solution is supplied to the chemical solution storage tank. Manufacturing method.   2. The method of manufacturing a semiconductor device according to claim 1, wherein the step (b) includes a step (b1) of heating the first chemical solution.   The said 1st chemical | medical solution is heated at the temperature of 70 degreeC or more and 90 degrees C or less in the said process (b1) for the time of 5 minutes or more and 15 minutes or less. A method for manufacturing a semiconductor device.   2. The method of manufacturing a semiconductor device according to claim 1, wherein the step (b) includes a step (b2) of irradiating the first chemical solution with UV light. In the step (b2), wherein the UV light is a wavelength of 100nm or more and 400nm or less, pulse energy - is at 0.1 J / cm ² or more and 10J / cm ² or less, the UV light or 1 minute and 15 6. The method of manufacturing a semiconductor device according to claim 5, wherein the irradiation is performed for a time equal to or less than a minute.   2. The method of manufacturing a semiconductor device according to claim 1, wherein the step (b) includes a step (b3) of heating the first chemical solution and irradiating the first chemical solution with UV light. . In the step (b3), the first chemical solution is heated at a temperature of 70 ° C. or more and 90 ° C. or less, the wavelength is 100 nm or more and 400 nm or less, and the pulse energy is 0.1 J / cm ² or more. The method of manufacturing a semiconductor device according to claim 7, wherein the UV light of 10 J / cm ² or less is irradiated for a time of 30 seconds or more and 10 minutes or less. The method of manufacturing a semiconductor device according to claim 5, wherein the UV light includes F ₂ light, ArF light, KrCl light, KrF light, XeCl light, or XeF light.   The method for manufacturing a semiconductor device according to claim 1, wherein the step (b) includes a step (b4) of measuring the absorbance of the first chemical solution.   The said 2nd chemical | medical solution is adjusted to desired temperature and desired density | concentration by mixing the said activated 1st chemical | medical solution and the said pure water in the said process (c). The manufacturing method of the semiconductor device of any one of 1-10.   The oxidizing agent includes at least one selected from the group consisting of nitric acid, hydrogen peroxide, ozone water, sulfuric acid, electrolytic sulfuric acid water, potassium permanganate, chromium trioxide, and osmium tetroxide. Item 12. The method for manufacturing a semiconductor device according to any one of Items 1 to 11.   The complexing agent is hydrochloric acid, calcium chloride, potassium chloride, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, hydroiodic acid, sodium iodide, potassium iodide, 13. At least one selected from the group consisting of calcium iodide, hydrobromic acid, sodium bromide, potassium bromide and calcium bromide, according to any one of claims 1 to 12, A method for manufacturing a semiconductor device.   The semiconductor device according to claim 1, wherein in the step (d), the second chemical solution is supplied to the semiconductor substrate at a temperature of 23 ° C. or more and 60 ° C. or less. Manufacturing method. In the step (a), the second chemical solution is adjusted using a nitric acid aqueous solution having a nitric acid concentration of 70%, a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 36%, and pure water,
The aqueous nitric acid solution, the aqueous hydrochloric acid solution and the pure water are in a volume ratio, and when the aqueous nitric acid solution is 1, the aqueous hydrochloric acid solution is 1 to 5 and the pure water is 3 to 500. The method for manufacturing a semiconductor device according to claim 1, wherein: A chemical preparation tank for mixing the oxidizing agent and the complexing agent to prepare the first chemical,
A chemical liquid storage tank for mixing the first chemical liquid prepared in the chemical liquid preparation tank with pure water to adjust a second chemical liquid diluted with the first chemical liquid, and storing the adjusted second chemical liquid;
A processing chamber for supplying the second chemical stored in the chemical storage tank to a semiconductor substrate housed therein;
The said chemical | medical solution preparation tank has the activation means to activate the said 1st chemical | medical solution, The manufacturing apparatus of the semiconductor device characterized by the above-mentioned.   The semiconductor device manufacturing apparatus according to claim 16, wherein the activating means is a heating mechanism.   18. The semiconductor device according to claim 17, wherein the heating mechanism heats the first chemical solution for a time of 5 minutes to 15 minutes and at a temperature of 70 ° C. to 90 ° C. 18. Manufacturing equipment.   17. The semiconductor device manufacturing apparatus according to claim 16, wherein the activating means is a UV light irradiation mechanism. The UV light irradiation mechanism applies UV light having a wavelength of 100 nm or more and 400 nm or less to the first chemical solution at a repetition frequency of 5 Hz or more and 600 kHz or less, an output of 2 W or more and 800 W or less, and 0.1 J / cm ^2. 20. The apparatus for manufacturing a semiconductor device according to claim 19, wherein the irradiation is performed at a pulse energy of 10 J / cm < ² > or less for a time of 1 minute or more and 15 minutes or less.   17. The semiconductor device manufacturing apparatus according to claim 16, wherein the activating means is a heating mechanism and a UV light irradiation mechanism. The heating mechanism heats the first chemical solution at a temperature of 70 ° C. or higher and 90 ° C. or lower,
The UV light irradiation mechanism applies UV light having a wavelength of 100 nm or more and 400 nm or less to the first chemical solution at a repetition frequency of 5 Hz or more and 600 kHz or less, an output of 2 W or more and 800 W or less, and 0.1 J / cm ^2. The apparatus for manufacturing a semiconductor device according to claim 21, wherein the irradiation is performed at a pulse energy of 10 J / cm ² or less for a time of 30 seconds or more and 10 minutes or less.