TWI410287B - Liquid processing device and processing liquid supply method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid treatment device capable of immediately and precisely measuring concentration of chemicals when the concentration of a treatment liquid containing two types of chemicals or more is measured and also, of precisely measuring the concentration of chemicals when the concentration of a treatment liquid containing relatively light concentration of chemicals is measured; and a treatment liquid supply method therefor. <P>SOLUTION: The liquid treatment device includes a treatment section 80 for treatment of an object to be treated by a treatment liquid; a supply passage 1 connected to the treatment section 80, for guiding a treatment liquid to the treatment section 80; a solvent supply section 7 for supplying a solvent to the supply passage 1; and a chemicals supply section 5 for supplying chemicals to the supply passage 1 through a chemicals supply passage 6 to produce chemicals diluted by the solvent. A measurement section 10 for measuring electrical conductivity of the chemicals diluted by the solvent is located on the downstream side of connection places 25a, 35a, 45a on the supply passage 1, to which the chemicals supply passage 6 is connected. An additional chemicals supply section 11 for supplying additional chemicals different from the chemicals is connected to the downstream side of a measurement place 10a at which the measurement section 10 is located out of the supply passage 1, through the additional chemicals supply passage 3. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

Liquid processing device and processing liquid supply method

The present invention relates to a liquid processing apparatus for measuring a concentration of a chemical solution contained in a processing liquid, a processing liquid for treating the object to be processed, and a processing liquid supply method for supplying the processing liquid to the object to be processed.

Conventionally, when cleaning a semiconductor wafer (hereinafter also referred to as a wafer) of a processed object, it is used for adding ammonia hydrogen peroxide water of NH ₄ OH (ammonium hydroxide) and hydrogen peroxide water to the pure water of the solvent. (SC1), or hydrochloric acid hydrogen peroxide water (SC2) containing hydrochloric acid and hydrogen peroxide water, or dilute hydrofluoric acid diluted with pure water by hydrofluoric acid, or the like.

Here, ammonia hydrogen peroxide water (SC1) is mainly used to remove particles adhering to the wafer, hydrogen peroxide water is mainly used to remove metal contamination of the wafer, and dilute hydrofluoric acid is mainly used to remove wafer contamination. .

In order to determine the concentration of a chemical solution contained in such a treatment liquid of ammonia hydrogen peroxide (SC1) or hydrogen peroxide water (SC2) or dilute hydrofluoric acid, a method for measuring the conductivity of the treatment liquid is known. Or a method of measuring the transmittance of light passing through the treatment liquid (absorbance of the treatment liquid) (see Patent Document 1, Patent Document 2, and Patent Document 3).

[Patent Document 1] Japanese Patent Laid-Open No. 62-8040

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-154683

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-189207

However, as described above, the ammonia hydrogen peroxide water (SC1) contains two kinds of chemical solutions of NH ₄ OH and hydrogen peroxide water, and similarly, hydrochloric acid hydrogen peroxide (SC2) contains hydrochloric acid and hydrogen peroxide. Water 2 kinds of chemical solutions.

Therefore, when the conductivity of the treatment liquid is measured and the concentration of the chemical solution is measured, it is difficult that the conductive effect caused by one of the chemical solutions is mixed with the conductive effect caused by the other chemical solution. Determine the exact concentration of each chemical solution. Further, when the transmittance of the light of the treatment liquid (the absorbance of the treatment liquid) is measured and the concentration of the chemical solution is measured, the concentration of each chemical solution can be accurately measured, but the measurement time is time-consuming.

Further, in the case of using a treatment liquid containing a relatively concentrated chemical solution, that is, when the amount of the chemical solution to be supplied is large, the concentration of the chemical solution can be measured by directly measuring the flow rate of the supplied chemical solution. However, in the case of using a treatment liquid containing a chemical solution having a lower concentration, since the amount of the chemical solution supplied is small, it is extremely difficult to accurately measure the flow rate of the supplied chemical solution.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid processing apparatus capable of rapidly and accurately measuring the concentration of a chemical solution when measuring the concentration of a treatment liquid containing two or more kinds of chemical solutions, and determining the concentration of the chemical solution. When the concentration of the treatment liquid of the low-concentration chemical solution is used, the concentration of the chemical solution can be accurately measured, and a treatment liquid supply method for supplying the treatment liquid to the object to be processed can be provided.

The liquid processing apparatus according to the present invention processes the object to be processed by using a treatment liquid produced by mixing a solvent with a chemical solution; characterized by comprising:

a processing unit that processes the object to be processed by the treatment liquid;

a supply passage connected to the processing unit to guide the processing liquid to the processing unit;

a solvent supply unit that supplies the solution to the supply channel;

The chemical solution supply unit supplies the chemical solution to the supply channel via the chemical solution supply channel, and generates a solvent-diluted chemical solution;

The measuring unit is disposed on the downstream side of the connection portion to which the chemical solution supply channel is connected in the supply channel, and measures the conductivity of the chemical solution diluted by the solvent;

The additional chemical solution supply unit is connected to the downstream side of the measurement site provided in the measurement unit in the supply channel, and supplies an additional chemical solution different from the chemical solution via the additional chemical solution supply channel.

In this manner, a measurement unit that measures the conductivity is provided on the downstream side of the connection portion to which the chemical solution supply channel is connected in the supply channel, and is provided on the downstream side of the measurement portion provided in the measurement unit in the supply channel. In addition, an additional chemical solution supply unit that supplies an additional chemical solution different from the chemical solution via the additional chemical solution supply channel is connected, and therefore, when the concentration of the treatment liquid containing two or more kinds of chemical solutions is measured, The concentration of the chemical solution is quickly and accurately determined. Further, when the cleaning solution contains a chemical solution having a relatively low concentration, that is, when the amount of the chemical solution to be supplied is small, the amount of the chemical solution supplied from the measuring unit for measuring the conductivity can be accurately measured.

In the liquid processing apparatus according to the present invention, the chemical solution supply unit is added, and hydrogen peroxide is preferably supplied as the additional chemical solution.

Preferably, the liquid processing apparatus according to the present invention further includes: a calculating unit that calculates a concentration of the chemical solution supplied from the chemical solution supply unit based on a conductivity measured by the measuring unit;

The adjustment unit adjusts the amount of the chemical solution supplied from the chemical solution supply unit based on the concentration of the chemical solution calculated by the calculation unit.

With such a configuration, the concentration of the chemical solution supplied from the chemical solution supply unit can be adjusted at any time, and the concentration of the chemical solution can be quickly brought to an appropriate concentration.

Preferably, the liquid processing apparatus according to the present invention further includes a concentration equalizing unit provided between the connection portion of the supply channel in which the chemical solution supply channel is connected and the measurement portion provided in the measurement unit to cause solvent and chemistry The drug solution is mixed and homogenized.

According to such a configuration and measurement unit, the conductivity of the solvent-diluted chemical solution can be measured with good precision, and the measurement result can be quickly provided.

In the above-described liquid processing apparatus, it is preferable that the measurement unit provides a measurement result of the electrical conductivity within 0.5 second after the chemical solution diluted with the solvent passes through the measurement unit.

According to the method of supplying a treatment liquid according to the present invention, a treatment liquid obtained by mixing a solvent and a chemical solution is supplied to a target object; and the method comprises the steps of:

a solvent supply step of supplying a solvent to the supply channel;

a chemical solution supply step of supplying a chemical solution to the supply channel and generating a chemical solution diluted with the solvent;

a measuring step of determining a concentration of the chemical solution supplied in the chemical solution supply step by measuring a conductivity of the chemical solution diluted by the solvent;

An additional chemical solution supply step of supplying a chemical solution that is diluted with a solvent to an additional chemical solution different from the chemical solution to generate a treatment liquid;

In the substrate processing step, the treatment liquid is supplied to the object to be processed.

According to such a method, since the concentration of the chemical solution supplied in the chemical solution supply step is measured by measuring the conductivity of the chemical solution diluted with the solvent, the additional chemical is supplied to the chemical solution diluted with the solvent. Since the treatment liquid is generated by the solution, when the concentration of the treatment liquid containing two or more kinds of chemical solutions is measured, the concentration of the chemical solution can be quickly and accurately measured. Further, when the cleaning liquid contains a chemical solution having a relatively low concentration, that is, when the amount of the chemical solution to be supplied is small, the amount of the chemical solution supplied from the measuring unit for measuring the conductivity can be accurately measured.

According to the present invention, since the conductivity of the chemical solution diluted with the solvent is measured, an additional chemical solution different from the chemical solution is supplied, so that the concentration of the treatment liquid containing two or more kinds of chemical solutions can be quickly measured. When the concentration of the chemical solution is accurately measured and the concentration of the treatment liquid containing the chemical solution having a lower concentration is measured, the concentration of the chemical solution can be accurately determined.

(Best form of implementing the invention) Implementation form

Hereinafter, embodiments of the liquid processing apparatus and the processing liquid supply method of the present invention will be described with reference to the drawings. Here, Fig. 1 is a view showing a schematic configuration of a liquid processing apparatus according to an embodiment of the present invention.

The liquid processing apparatus according to the present embodiment is for processing a semiconductor wafer (hereinafter also referred to as a wafer W) as a target object, and is treated by using a processing liquid generated by mixing a solvent and a chemical solution.

The liquid processing apparatus shown in Fig. 1 includes a processing unit 80 that processes the wafer W with a processing liquid, a supply channel 1 that is coupled to the processing unit 80, and directs the processing liquid to the processing unit 80, and a solvent supply unit 7 for the supply channel. 1 The solvent is supplied; the chemical solution supply unit 5 supplies the chemical solution to the supply channel 1 via the chemical solution supply channel 6.

The processing unit 80 includes a case 81, a holding portion 82 that is provided in the case 81, holds the wafer W, and a processing liquid supply unit 83 for the surface (top surface) of the wafer W held by the holding portion 82. The processing liquid is supplied to the back surface processing liquid supply unit 84, and the processing liquid is supplied to the back surface (bottom surface) of the wafer W.

Further, as shown in Fig. 1, the chemical solution supply unit 5 has a hydrofluoric acid supply unit 21 and supplies hydrofluoric acid; a hydrochloric acid supply unit 31 supplies hydrochloric acid; and an NH ₄ OH supply unit 41 supplies NH ₄ OH (hydrogen). Ammonium oxide).

Further, as shown in Fig. 1, the chemical solution supply passage 6 has a hydrofluoric acid supply passage 25, and the hydrofluoric acid supplied from the hydrofluoric acid supply unit 21 is introduced into the supply passage 1; the hydrochloric acid supply passage 35 is supplied with hydrochloric acid. introducing a supply of the supply passage 31 supplying portion hydrochloride; NH2 ₄ OH supply passage 45, supplied from the NH NH ₄ OH ₄ OH supplying portion 41 is introduced into the supply passage 1.

Further, as shown in FIG. 1, the hydrofluoric acid supply passage 25 connected to the hydrofluoric acid supply unit 21 is provided with a hydrofluoric acid regulator 22 for adjusting the flow rate of hydrofluoric acid flowing through the hydrofluoric acid supply passage 25. Similarly, the supply of hydrochloric acid portion hydrochloride supply passage 31 connected to the 35, is provided to adjust the flow 32, and NH2 ₄ OH supplying section NH 41 concatenate ₄ OH supply passage 45 to the regulator hydrochloric flow rate of the hydrochloric acid supply passage acid 35, the 45 is provided to adjust the flow to the flow rate of the NH ₄ OH NH ₄ OH NH ₄ OH feed channel regulator 42.

Moreover, as shown in FIG. 1, the hydrofluoric acid supply passage 25 is connected to the supply passage 1 at the connection portion 25a via the hydrofluoric acid supply valve 24 that is openable and closable on the downstream side of the hydrofluoric acid regulator 22. Similarly, the hydrochloric acid supply passage 35 is connected to the supply passage 1 at the joint portion 35a via the open/closed hydrochloric acid supply valve 34 on the downstream side of the hydrochloric acid regulator 32, and the NH ₄ OH supply passage 45 is disposed in the NH ₄ OH regulator 42. The downstream side is connected to the supply passage 1 at the joint portion 45a via the NH ₄ OH supply valve 44 that is openable and closable.

Further, as shown in Fig. 1, the solvent supply unit 7 has a DIW supply unit 61, supplies pure water (DIW) to the supply channel 1, and heats the DIW supply unit 66, and supplies the pure water heated by the heating unit 66a to the supply channel 1 ( DIW).

Further, as shown in FIG. 1, on the downstream side of the DIW supply portion 61 of the supply passage 1, a pure water regulator 62 for adjusting the flow rate of pure water flowing in the supply passage 1 is provided. Further, on the downstream side of the pure water regulator 62, a pure water flow meter 63 for measuring the flow rate of pure water flowing in the supply passage 1 is provided. Further, similarly, on the downstream side of the heating DIW supply unit 66 of the supply passage 1, a heated pure water regulator 67 for adjusting the flow rate of the heated pure water in the supply passage 1 is provided, and the heated pure water regulator is provided. On the downstream side of 67, a heated pure water flow meter 68 for measuring the flow rate of the heated pure water flowing in the supply passage 1 is provided. Further, on the downstream side of the pure water flow meter 63 and the heated pure water flow meter 68, a pure water supply valve 64 that is openable and closable is provided.

Moreover, as shown in FIG. 1, the pure water flow meter 63 is connected to the adjustment part 52 of the control part 50 mentioned later, and this adjustment part 52 is connected to the pure water regulator 62. Further, similarly, the heated pure water flow meter 68 is connected to the adjustment unit 52 of the control unit 50, and the adjustment unit 52 is connected to the heated pure water regulator 67.

Further, in the supply passage 1, the downstream side of the connection portions 25a, 35a, 45a to which the chemical solution supply passage 6 (the hydrofluoric acid supply passage 25, the hydrochloric acid supply passage 35, and the NH ₄ OH supply passage 45) are connected is provided. The measuring unit 10 for measuring the conductivity of the chemical solution diluted with the pure water of the solvent is measured.

Further, as shown in FIG. 1, the measurement unit 10 is connected to the measurement unit 10, and the calculation unit 51 calculates the concentration of the chemical solution supplied from the chemical solution supply unit 5 based on the conductivity measured by the measurement unit 10. Further, the calculation unit 51 is connected to the adjustment unit 52, and the adjustment unit 52 is supplied from the chemical solution supply unit 5 (the hydrofluoric acid supply unit 21 and the hydrochloric acid supply unit 31 in accordance with the concentration of the chemical solution calculated by the calculation unit 51. The amount of the chemical solution supplied to the NH ₄ OH supply unit 41) is adjusted using a regulator (a hydrofluoric acid regulator 22, a hydrochloric acid regulator 32, and an NH ₄ OH regulator 42). Further, the calculation unit 51 and the adjustment unit 52 constitute the control unit 50.

Further, as shown in FIG. 1, in the supply passage 1, the connection portion 3a on the downstream side of the measurement site 10a provided in the measurement unit 10 is connected to a hydrogen peroxide water supply unit (additional chemical solution supply unit) 11, which The hydrogen peroxide water supply unit (additional chemical solution supply unit) 11 supplies hydrogen peroxide (additional chemicals) different from the chemical solution supplied from the chemical solution supply unit 5 via the additional chemical solution supply channel 3 Solution).

Further, as shown in FIG. 1, a hydrogen peroxide water regulator 12 is provided in the additional chemical solution supply passage 3, and the hydrogen peroxide water regulator 12 adjusts hydrogen peroxide flowing in the additional chemical solution supply passage 3. Traffic. Further, on the downstream side of the hydrogen peroxide water regulator 12, a hydrogen peroxide water flow meter 13 for measuring the flow rate of hydrogen peroxide flowing in the additional chemical solution supply passage 3 is provided. Further, the hydrogen peroxide water flow meter 13 is connected to the adjustment unit 52 of the control unit 50, and the hydrogen peroxide water regulator 12 is connected to the adjustment unit 52.

Moreover, as shown in FIG. 1, the hydrogen peroxide water storage tank 17 is connected between the hydrogen peroxide water supply part 11 and the hydrogen peroxide water regulator 12. Further, by opening the first hydrogen peroxide water supply valve 15 and closing the second hydrogen peroxide water supply valve 16, hydrogen peroxide can be supplied from the hydrogen peroxide water supply unit 11 to the hydrogen peroxide water storage tank 17, and By opening the second hydrogen peroxide water supply valve 16 and closing the first hydrogen peroxide water supply valve 15, the hydrogen peroxide water stored in the hydrogen peroxide water storage tank 17 can be supplied to the substrate processing apparatus.

Further, a hydrogen gas supply unit 71 is connected to the hydrogen peroxide water storage tank 17, and a predetermined pressure is applied to the hydrogen peroxide stored in the hydrogen peroxide water storage tank 17 via the nitrogen gas supply passage 79. Further, a nitrogen gas regulator 72 for adjusting the amount of nitrogen gas supplied from the nitrogen gas supply unit 71 is provided in the nitrogen gas supply passage 79 between the nitrogen gas supply unit 71 and the hydrogen peroxide water storage tank 17.

Further, as shown in Fig. 1, on the downstream side of the nitrogen regulator 72, a nitrogen supply valve 75 for supplying nitrogen gas to the hydrogen peroxide water storage tank 17 and a nitrogen gas discharge valve 76 for discharging nitrogen gas are provided. To the outside. Further, the nitrogen gas discharge valve 76 communicates with a discharge port (not shown) that discharges nitrogen gas to the outside.

Further, when nitrogen gas is supplied to the hydrogen peroxide water storage tank 17, and hydrogen peroxide in the hydrogen peroxide water storage tank 17 is supplied to the supply passage 1, the nitrogen gas supply valve 75 is opened and the nitrogen gas discharge valve 76 is closed. Further, at this time, the first hydrogen peroxide water supply valve 15 is closed, and the second hydrogen peroxide water supply valve 16 and the hydrogen peroxide water supply valve 14 are opened.

On the other hand, when nitrogen gas is discharged from the hydrogen peroxide water storage tank 17, and hydrogen peroxide from the additional chemical solution supply unit 11 is supplied into the hydrogen peroxide water storage tank 17, the nitrogen gas supply valve 75 is closed and the nitrogen gas discharge valve is closed. 76 opens. Further, at this time, the first hydrogen peroxide water supply valve 15 is opened and the second hydrogen peroxide water supply valve 16 is closed.

Further, in the supply passage 1, between the connection portions 25a, 35a, and 45a to which the chemical solution supply passage 6 is connected and the measurement portion 10a provided in the measurement unit 10, a solvent and a chemical solution are uniformly mixed as static. The concentration of the mixer is uniform (concentration equalization unit) 90.

Next, the action of this embodiment obtained by such a configuration will be described.

First, the cleaning liquid is sometimes used when it is diluted with pure water to a lower concentration of NH ₄ OH (for example, NH ₄ OH: pure water = 1:100).

First, the pure water supply valve 64 is opened, and pure water which is a solvent is supplied to the supply passage 1 (solvent supply step). At this time, the flow rate of the pure water flowing in the supply passage 1 is measured by the pure water flow meter 63, and the flow is adjusted by the pure water regulator 62 in accordance with the instruction from the adjustment unit 52 in accordance with the measured pure water flow rate. Supply pure water flow in channel 1. Further, similarly, the flow rate of the heated pure water flowing in the supply passage 1 is measured by heating the pure water flow meter 68, and in accordance with the measured flow rate of the heated pure water, in accordance with an instruction from the adjustment unit 52, The flow rate of the heated pure water flowing in the supply passage 1 is adjusted by the heated pure water regulator 67, and at the same time, the pure water flowing in the supply passage 1 is adjusted (the pure water supplied from the DIW supply unit 61 and the supplied from the DIW supply unit) The temperature of the mixture of heated pure water supplied).

Next, the NH ₄ OH supply valve 44 is opened, and the chemical solution NH ₄ OH is supplied to the supply passage 1 via the NH ₄ OH supply passage 45 (chemical solution supply step).

Next, NH ₄ OH and pure water simultaneously reach a concentration uniform tube 90 such as a static mixer, and the uniform tube 90 is mixed with pure water to form a uniform (homogeneization step).

Next, the conductivity of the NH ₄ OH diluted with pure water is measured by the measuring unit 10 (measurement step). Here, as described above, the NH ₄ OH and the pure water are uniformly mixed by the uniform concentration tube 90. Therefore, the measurement unit 10 can measure the conductivity of the NH ₄ OH diluted with pure water with good precision. In this way, since the measurement unit 10 can quickly provide the measurement result to the calculation unit 51 to be described later, it is preferable to provide the measurement unit 10, which can be in pure water. The measurement result of the conductivity was supplied to the calculation unit 51 within 0.5 second after the passage of the diluted NH ₄ OH.

Next, the calculation unit 51 of the control unit 50 calculates the concentration of the diluted NH ₄ OH based on the conductivity measured by the measurement unit 10. Thereafter, the calculation unit 51 calculates the flow rate from the NH4OH supply unit 41 using the calculated concentration of the diluted NH ₄ OH and the flow rate of the pure water derived from the pure water flow meter 63 and the heated pure water flow meter 68. The concentration of NH ₄ OH (calculation step).

In this manner, the cleaning liquid diluted with pure water using lower concentrations of the case of NH ₄ OH, NH supplied from the supply portion of NH ₄ OH 41 ₄ OH in very small amounts. Therefore, for example, even if the flow meter is disposed on the supply passage 45, the flow rate cannot be accurately measured. Therefore, the exact concentration of NH ₄ OH diluted with pure water cannot be known. On the other hand, according to the present embodiment, the NH ₄ OH is diluted with pure water, and the concentration of the chemical solution (diluted NH ₄ OH) having an increased capacity is measured using the measuring unit 10 for measuring the conductivity. Thus, in this manner, even if the supply of the NH ₄ OH NH ₄ OH feed portion 41 in very small amounts, can also accurately determine the amount of NH ₄ OH NH ₄ OH supplied from the supply portion 41.

Further, the measurement unit 10 does not measure the light transmittance (absorbance of NH ₄ OH) of the diluted NH ₄ OH, and measures the conductivity. Therefore, the concentration of NH ₄ OH can be quickly detected as compared with the case of measuring the transmittance of light.

As described above, when using the calculation unit 51 calculates the concentration of NH ₄ OH NH ₄ OH feed the supply unit 41, is calculated by the control unit NH 50 of the adjusting unit 52, depending on the concentration of ₄ OH, NH ₄ OH to adjust Regulator 42. Therefore, the NH ₄ OH concentration supplied from the NH ₄ OH supply unit 41 to the supply channel 1 can be adjusted at any time, and the concentration of the NH ₄ OH can be quickly brought to an appropriate concentration.

Next, NH ₄ OH diluted with pure water is supplied to the treatment liquid supply unit 83 and the back surface treatment liquid supply unit 84 of the treatment unit 80 (substrate treatment step). Here, the NH ₄ OH which is accurately calculated as described above is adjusted to an appropriate concentration of NH ₄ OH to supply the wafer W, so that the wafer W can be processed with good precision.

(Using ammonia hydrogen peroxide water (SC1) treatment), secondly, the cleaning solution is produced using a concentrated concentration of NH ₄ OH (for example, ammonia water: hydrogen peroxide water: water = 1:1:5 (capacity ratio)) Ammonia hydrogen peroxide water (SC1) is used to clean the wafer W.

First, the pure water supply valve 64 is opened, and pure water which is a solvent is supplied to the supply passage 1 (solvent supply step). At this time, the flow rate of the pure water flowing in the supply passage 1 is measured by the pure water flow meter 63, and the supply passage is adjusted by the pure water regulator 62 in accordance with the instruction from the adjustment unit 52 in accordance with the measured pure water flow rate. The flow of pure water flowing in 1 . Further, similarly, the flow rate of the heated pure water flowing in the supply passage 1 is measured by the heated pure water flow meter 68, and the flow rate of the heated pure water measured is used in accordance with an instruction from the adjustment unit 52. The heated pure water regulator 67 adjusts the flow rate of the heated pure water flowing in the supply passage 1, and at the same time, adjusts the pure water flowing in the supply passage 1 (pure water supplied from the DIW supply unit 61 and supplied from the heated DIW supply unit) The temperature of the mixture of heated pure water).

Next, the NH ₄ OH supply valve 44 is opened, and the chemical solution NH ₄ OH is supplied to the supply channel 1 via the NH ₄ OH supply passage 45 (chemical solution supply step).

At this time, the second hydrogen peroxide water supply valve 16 and the hydrogen peroxide water supply valve 14 are opened, and the hydrogen peroxide water stored in the hydrogen peroxide water storage tank 17 is supplied to the supply channel 1 (additional chemical solution supply) step).

Further, at this time, the nitrogen gas supply valve 75 is opened, but the nitrogen gas discharge valve 76 is closed, and the hydrogen peroxide supplied from the hydrogen gas supply unit 17 is applied to the hydrogen peroxide stored in the hydrogen peroxide water storage tank 17 by the pressure of the nitrogen gas supplied from the nitrogen gas supply unit 71. pressure. In this manner, hydrogen peroxide water is stored in the hydrogen peroxide water storage tank 17 having a small capacity, and hydrogen peroxide water is supplied to the hydrogen peroxide water by applying a pressure of nitrogen gas, so that the peroxidation of the supply can be easily adjusted. The amount of hydrogen water.

Next, the conductivity of the NH ₄ OH diluted with pure water is measured by the measuring unit 10 (measurement step). Next, the calculation unit 51 of the control unit 50 calculates the concentration of the diluted NH ₄ OH based on the conductivity measured by the measurement unit 10. Thereafter, the calculation unit 51 calculates the supply of the NH ₄ OH supply unit 41 using the calculated diluted NH ₄ OH concentration and the pure water flow rate derived from the pure water flow meter 63 and the heated pure water flow meter 68. NH ₄ OH concentration (calculation step).

In this manner, according to the present embodiment, the measurement unit 10 can be, without adding to the hydrogen peroxide over state, detecting NH NH ₄ OH supplied from the supply portion 41 of the conductivity ₄ OH. Thus, the measurement can be added to the non-conductive effects induced by hydrogen peroxide, measured from only due to NH ₄ OH-induced effect of the conductivity of the conductive, can accurately calculate the concentration of NH ₄ OH.

Further, as in the conventional case where the electrical conductivity, and NH ₄ OH in a mixed state over the hydrogen peroxide was measured from the amount of NH ₄ OH ₄ OH NH supply portion when a small amount of, the more small, from the hydrogen peroxide through the conductive The greater the contribution of the effect. Accordingly, as shown in the present embodiment, can be determined only from ₄ OH NH2 induced effect of the conductivity of the conductive, refers to the amount of supply of ₄ OH NH ₄ OH NH supply portion is a small amount of the less as compared In the conventional method, the more beneficial.

Further, the measuring unit 10 does not measure the light transmittance (absorbance of NH ₄ OH) of the diluted NH ₄ OH, and measures the conductivity. Therefore, the concentration of NH ₄ OH can be quickly detected as compared with the case of measuring the light transmittance.

As described above, when the calculation unit 51 calculates the NH ₄ OH concentration supplied from the NH ₄ OH supply unit 41, the adjustment unit 52 of the control unit 50 adjusts the NH ₄ OH regulator 42 based on the calculated NH ₄ OH concentration. Therefore, the NH ₄ OH concentration supplied from the NH ₄ OH supply unit 41 to the supply channel 1 can be adjusted at any time, and the concentration of the NH ₄ OH can be quickly brought to an appropriate concentration.

On the other hand, the hydrogen peroxide water discharged from the hydrogen peroxide water storage tank 17 is used to measure the concentration of the diluted NH ₄ OH in the measuring unit 10 as described above, and the calculation unit 51 calculates the supply from the NH ₄ OH supply unit 41. NH ₄ OH concentration, and the adjusting portion 52 to adjust the supply of NH ₄ OH during the amount of use of hydrogen peroxide in a flow meter 13 measuring the flow through the flow 3 of hydrogen peroxide water supply passage, while the basis of hydrogen peroxide was determined through The flow rate of water is adjusted by the hydrogen peroxide water regulator 12 in accordance with an instruction from the adjustment unit 52.

Next, the NH ₄ OH is diluted to an appropriate concentration as described above, and the flow-adjusted hydrogen peroxide water as described above is mixed, and in the supply channel 1, ammonia hydrogen peroxide water (SC1) as a treatment liquid is produced.

Then, the ammonia hydrogen peroxide water (SC1) is supplied to the processing liquid supply unit 83 and the back surface processing liquid supply unit 84 of the processing unit 80 (substrate processing step). Here, since the ammonia hydrogen peroxide water (SC1) adjusted to an appropriate concentration is supplied to the wafer W in accordance with the accurately calculated NH ₄ OH concentration as described above, the wafer W can be processed with good precision.

That is, at the time of the previously processed very small amount of NH ₄ OH supplied from the supply portion 41 NH ₄ OH description, when there are more chemical processing amount ₄ OH mixed solution of hydrogen peroxide and water with NH, The concentration of the treatment liquid can be accurately determined.

(Treatment by Hydrogen Peroxide Water (SC2)) When the wafer W is washed with hydrogen peroxide water (SC2) as a treatment liquid, it is substantially the same as the treatment using the above-described ammonia hydrogen peroxide water (SC1). In other words, the opening and closing of the NH ₄ OH supply valve 44 may be changed to the opening and closing of the hydrochloric acid supply valve 34, and the other points are substantially the same as the treatment using the ammonia hydrogen peroxide water (SC1). Therefore, the detailed description is omitted.

According to the present embodiment, hydrochloric acid diluted to a lower concentration is used as the cleaning liquid, and even if the amount of hydrochloric acid supplied from the hydrochloric acid supply unit 31 is extremely small, the chemical solution in which the capacity is increased by diluting hydrochloric acid with pure water can be used (after dilution) The concentration of hydrochloric acid was measured using the measuring unit 10 for measuring the conductivity. Therefore, the amount of hydrochloric acid supplied from the hydrochloric acid supply unit 31 can be accurately measured.

Moreover, even when the wafer W is washed with hydrogen peroxide water (SC2), the conductivity of hydrochloric acid supplied from the hydrochloric acid supply unit 31 can be detected without adding hydrogen peroxide. Therefore, the conductivity of the conductive effect caused by only hydrochloric acid can be detected without adding the conductivity effect by hydrogen peroxide, and the concentration of hydrochloric acid can be accurately calculated. As a result, an accurate amount of hydrochloric acid can be supplied to the treatment unit 80, and the wafer W can be treated with hydrochloric acid hydrogen peroxide (SC2) composed of an accurate hydrochloric acid concentration.

Further, the measuring unit 10 does not measure the light transmittance (absorbance of hydrochloric acid) of the diluted hydrochloric acid, and measures the electrical conductivity. Therefore, the concentration of hydrochloric acid can be quickly detected as compared with the case of measuring the light transmittance.

(treatment with dilute hydrofluoric acid)

The case where the wafer W is washed using dilute hydrofluoric acid as a treatment liquid is substantially the same as the above treatment using ammonia hydrogen peroxide water (SC1) except that hydrogen peroxide water is not used. In other words, the NH ₄ OH supply valve 44 and the hydrogen peroxide water supply valve 14 are opened and closed, and the hydrofluoric acid supply valve 24 can be opened and closed, and the other points are substantially the same as those of the ammonia hydrogen peroxide water (SC1). Therefore, the detailed explanation is omitted.

Further, in the case where the wafer W is washed with dilute hydrofluoric acid, since the additional chemical solution hydrogen peroxide water is not used, the diluted hydrofluoric acid diluted with pure water becomes the treatment liquid.

1. . . Supply channel

3. . . Hydrogen peroxide water supply channel

3a. . . Joint site

5. . . Chemical solution supply department

6. . . Chemical solution supply channel

7. . . Solvent supply unit

10. . . Measurement department

10a. . . Measuring site

11. . . Additional chemical solution supply department

12. . . Hydrogen peroxide water regulator

13. . . Hydrogen peroxide water flow meter

14. . . Hydrogen peroxide water supply valve

15. . . First hydrogen peroxide water supply valve

16. . . Second hydrogen peroxide water supply valve

17. . . Hydrogen peroxide water storage tank

twenty one. . . Hydrofluoric acid supply

twenty two. . . Hydrofluoric acid regulator

twenty four. . . Hydrofluoric acid supply valve

25. . . Hydrofluoric acid supply channel

25a. . . Joint site

31. . . Hydrochloric acid supply department

32. . . Hydrochloric acid regulator

34. . . Hydrochloric acid supply valve

35. . . Hydrochloric acid supply channel

35a. . . Joint site

41. . . NH ₄ OH supply department

42. . . NH ₄ OH regulator

44. . . NH ₄ OH supply valve

45. . . NH ₄ OH supply channel

45a. . . Joint site

50. . . Control department

51. . . Computing department

52. . . Adjustment department

61. . . DIW Supply Department

62. . . Pure water regulator

63. . . Pure water flow meter

64. . . Pure water supply valve

66. . . Heating DIW supply department

66a. . . Heating department

67. . . Heating pure water regulator

68. . . Heating pure water flow meter

71. . . Nitrogen supply unit

72. . . Nitrogen regulator

75. . . Nitrogen supply valve

76. . . Nitrogen discharge valve

79. . . Nitrogen supply channel

80. . . Processing department

81. . . case

82. . . Holding unit

83. . . Treatment liquid supply unit

84. . . Back treatment liquid supply unit

90. . . Uniform concentration tube (concentration equalization section)

W. . . Wafer (processed object)

Fig. 1 is a view showing the schematic configuration of a liquid processing apparatus according to an embodiment of the present invention.

1. . . Supply channel

3. . . Hydrogen peroxide water supply channel

3a. . . Joint site

5. . . Chemical solution supply department

6. . . Chemical solution supply channel

7. . . Solvent supply unit

10. . . Measurement department

10a. . . Measuring site

11. . . Additional chemical solution supply department

12. . . Hydrogen peroxide water regulator

13. . . Hydrogen peroxide water flow meter

14. . . Hydrogen peroxide water supply valve

15. . . First hydrogen peroxide water supply valve

16. . . Second hydrogen peroxide water supply valve

17. . . Hydrogen peroxide water storage tank

twenty one. . . Hydrofluoric acid supply

twenty two. . . Hydrofluoric acid regulator

twenty four. . . Hydrofluoric acid supply valve

25. . . Hydrofluoric acid supply channel

25a. . . Joint site

31. . . Hydrochloric acid supply department

32. . . Hydrochloric acid regulator

34. . . Hydrochloric acid supply valve

35. . . Hydrochloric acid supply channel

35a. . . Joint site

41. . . NH ₄ OH supply department

42. . . NH ₄ OH regulator

44. . . NH ₄ OH supply valve

45. . . NH ₄ OH supply channel

45a. . . Joint site

50. . . Control department

51. . . Computing department

52. . . Adjustment department

61. . . DIW Supply Department

62. . . Pure water regulator

63. . . Pure water flow meter

64. . . Pure water supply valve

66. . . Heating DIW supply department

66a. . . Heating department

67. . . Heating pure water regulator

68. . . Heating pure water flow meter

71. . . Nitrogen supply unit

72. . . Nitrogen regulator

75. . . Nitrogen supply valve

76. . . Nitrogen discharge valve

79. . . Nitrogen supply channel

80. . . Processing department

81. . . case

82. . . Holding unit

83. . . Treatment liquid supply unit

84. . . Back treatment liquid supply unit

90. . . Uniform concentration tube (concentration equalization section)

W. . . Wafer (processed object)

Claims (8)

A liquid processing apparatus that processes a target object by using a treatment liquid produced by mixing a solvent and a chemical solution, and includes: a treatment unit that processes the object to be processed by the treatment liquid; and a supply passage that is coupled to the treatment unit; The processing liquid is guided to the processing unit; the solvent supply unit supplies the solvent to the supply channel; the chemical solution supply unit supplies the chemical solution to the supply channel via the chemical solution supply channel, and generates a solvent-diluted chemical solution; The measurement unit is provided on the downstream side of the connection portion to which the chemical solution supply channel in the supply channel is connected, for measuring the conductivity of the solvent solution diluted with the solvent, and the additional chemical solution supply unit is connected to the supply channel. The downstream side of the measurement site provided by the measurement unit supplies an additional chemical solution different from the chemical solution to the chemical solution diluted with the solvent via the additional chemical solution supply channel; the solvent flow meter is provided in the supply channel The solvent flow meter is used to measure the flow of the solvent flowing through the supply passage An additional chemical solution flow meter is provided in the additional chemical solution supply channel for measuring only the flow rate of the additional chemical solution flowing through the additional chemical solution supply channel; and the adjustment unit The amount of the chemical solution supplied from the chemical solution supply unit is adjusted in accordance with the conductivity measured by the measuring unit, and is adjusted from the solvent supply unit to the supply channel based on the flow rate of the solvent measured by the solvent flow meter. The amount of the solvent and the amount of the additional chemical solution supplied from the additional chemical solution supply unit to the additional chemical solution supply channel are adjusted according to the flow rate of the additional chemical solution measured by the additional chemical solution flow meter; The additional chemical solution adjusted by the additional chemical solution flowmeter is supplied to the solvent-diluted chemical solution adjusted by the measurement unit and the solvent flowmeter. The liquid processing apparatus according to claim 1, wherein the additional chemical solution supply unit supplies hydrogen peroxide as an additional chemical solution. The liquid processing apparatus according to claim 1 or 2, further comprising: a concentration equalizing unit disposed between the joint portion of the chemical solution supply passage provided in the supply passage and the measurement portion provided by the measuring portion To mix and homogenize the solvent with the chemical solution. The liquid processing apparatus according to claim 1 or 2, wherein the measuring unit provides a measurement result of the electrical conductivity within 0.5 second after the chemical solution diluted with the solvent passes through the measuring unit. A processing liquid supply method for supplying a treatment liquid produced by mixing a solvent and a chemical solution to a target object; characterized by comprising the steps of: a solvent supply step of supplying a solvent to a supply channel; and a chemical solution supply step, supplying The channel supplies a chemical solution and generates a solvent-diluted chemical solution; and the measuring step determines the conductivity of the chemical solution diluted by the solvent by measuring the conductivity of the chemical solution diluted by the solvent in the supply step of the chemical solution a concentration of the drug solution; an additional chemical solution supply step, and a chemical solution diluted with the solvent is supplied with an additional chemical solution different from the chemical solution to generate a treatment liquid; and an adjustment step is performed according to the measurement step The conductivity is adjusted to the amount of the chemical solution supplied in the chemical solution supply step; the solvent flow measuring step uses the solvent flow meter to measure the flow rate of the solvent flowing through the supply channel; the solvent flow rate adjusting step is based on the solvent The solvent measured in the flow measurement step The amount is adjusted to the amount of the solvent supplied in the solvent supply step; the chemical solution flow rate measuring step is added, and the chemical solution flow meter is added to measure only the additional chemical solution supplied in the additional chemical solution supply step. flow; The additional chemical solution flow rate adjusting step adjusts the amount of the additional chemical solution supplied in the additional chemical solution supply step based on the flow rate of the additional chemical solution measured in the additional chemical solution flow rate measuring step; a substrate processing step of supplying the treatment liquid to the object to be processed; and supplying an additional chemical solution adjusted according to the additional chemical solution flowmeter to the solvent-diluted by the measurement unit and the solvent flow meter Chemical solution. The processing liquid supply method according to claim 5, wherein the additional chemical solution supplied in the additional chemical solution supply step is hydrogen peroxide. The treatment liquid supply method according to claim 5, further comprising: a homogenization step of mixing and homogenizing the solvent and the chemical solution between the chemical solution supply step and the measurement step. According to the method of supplying a treatment liquid according to the fifth aspect of the invention, in the measuring step, the measurement result of the conductivity of the chemical solution diluted with the solvent is output within 0.5 second after the chemical solution diluted with the solvent passes through a measuring unit.