TW201936274A - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

A substrate processing method for selectively etching a tantalum nitride film by supplying a phosphoric acid aqueous solution containing germanium to a substrate having a hafnium oxide film and a tantalum nitride film exposed on the surface thereof. The method includes the steps of: storing a phosphoric acid aqueous solution containing a ruthenium having a predetermined ruthenium concentration range in a tank; supplying an aqueous phosphoric acid solution in the tank to the nozzle, and supplying the phosphoric acid aqueous solution to the substrate from the nozzle to process the substrate a step of recovering the aqueous solution of phosphoric acid used for the treatment of the substrate into the tank; a step of supplying the first aqueous solution of phosphoric acid containing the first aqueous solution of phosphoric acid containing the ruthenium to the tank; The second concentration having a low concentration includes a second phosphoric acid aqueous solution supply step in which the second aqueous phosphoric acid aqueous solution is supplied to the tank; and when the predetermined supplementary start condition is satisfied, the first determination step of the first and second aqueous phosphoric acid aqueous solution supply steps is started; And a supply amount determining step of determining the supply amount of the first and second phosphoric acid aqueous solutions.

Description

Substrate processing method and substrate processing device

Priority is claimed on Japanese Patent Application No. Hei. No. Hei. No. Hei. No. Hei.

The present invention relates to a method and apparatus for processing a substrate. The substrate to be processed includes, for example, a substrate for a FPD (Flat Panel Display) such as a semiconductor wafer, a liquid crystal display device, or an organic EL (Electroluminescence) display device, a substrate for a disk, and a disk. A substrate such as a substrate, a magneto-optical substrate, a photomask substrate, a ceramic substrate, or a solar cell substrate.

In the manufacturing steps of a semiconductor device or a liquid crystal display device, a substrate processing device for processing a substrate is used. Patent Document 1 discloses a substrate processing apparatus and a substrate processing method for supplying a phosphoric acid aqueous solution containing germanium to a substrate on which a hafnium oxide film and a tantalum nitride film are formed, and selectively etching the tantalum nitride film. The tantalum nitride film is etched by suppressing the etching of the hafnium oxide film by containing antimony in the aqueous phosphoric acid solution.

The substrate processing apparatus described in Patent Document 1 includes a rotary chuck that holds a substrate and rotates, first to third tanks that store phosphoric acid aqueous solution, and a new liquid supply device. Supplying phosphoric acid aqueous solution from the first tank toward the treatment liquid nozzle, from the treatment liquid nozzle The aqueous phosphoric acid solution to be discharged is supplied to the substrate held by the rotary chuck. When the liquid level of the first tank is lowered by the supply of the phosphoric acid aqueous solution, the phosphoric acid aqueous solution is supplied from the second tank to the first tank. On the other hand, the used phosphoric acid aqueous solution after being supplied to the substrate is recovered to the third tank. The concentration of phosphoric acid in the recovered aqueous phosphoric acid solution was measured by a phosphoric acid concentration meter. Based on the detection result, the phosphoric acid concentration adjustment operation by the supply of phosphoric acid, DIW (deionized water) or nitrogen gas is performed in the third tank. When the recovery operation is stopped, the concentration of rhodium in the recovered aqueous phosphoric acid solution is detected by a helium concentration meter. The new liquid supply device adjusts the ruthenium concentration of the phosphoric acid aqueous solution in the third recovery tank to the reference ruthenium concentration by adding the phosphoric acid aqueous solution to the third tank. More specifically, the new liquid supply device adjusts the detection result of the helium concentration meter to adjust the new liquid (unused phosphoric acid aqueous solution) whose concentration can be changed, and supplies the new liquid to the third tank. When the liquid level of the second tank is lowered to the lower limit level, the liquid path is switched so as to exchange the tasks of the second tank and the third tank, and the same operation is repeated.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2015-177139

The new liquid supply device can change the concentration of ruthenium in the new liquid to be replenished in accordance with the concentration of ruthenium in the recovered phosphoric acid aqueous solution. Therefore, it is necessary to prepare a new liquid having a different concentration each time it is replenished. The new liquid supply device has a krypton concentration meter, and the cesium concentration is measured by the krypton concentration meter, and a phosphoric acid aqueous solution (stock solution) and a hydrazine concentrate are introduced and mixed. By the introduction of the new liquid, the mixed liquid is disturbed, and accordingly, according to the concentration of the liquid The measurement results were disturbed. On the other hand, it takes a considerable time for the concentration of ruthenium in the mixed solution to be uniform and stable, so that it takes time to prepare the new liquid.

Further, since the enthalpy concentration is measured by stopping the liquid recovery in the third tank, and the enthalpy concentration of the new liquid is set accordingly, the new liquid is prepared, so that the new liquid cannot be prepared in advance. Therefore, even when a new liquid supplied to the reference concentration is sufficient, the standby time for the new liquid preparation is generated. If the liquid supply to the first tank is stagnated due to the standby time, the productivity of the substrate processing is affected.

Further, since the second tank, the third tank, and the new liquid supply device are required to have a helium concentration meter, the apparatus configuration is complicated, and the cost is increased accordingly.

According to an embodiment of the present invention, there is provided a substrate processing method and a substrate processing apparatus capable of stabilizing a germanium concentration in an aqueous phosphoric acid solution supplied to a substrate without impairing productivity of substrate processing. .

According to an embodiment of the present invention, there is provided a substrate processing method for selectively etching the tantalum nitride film by supplying a phosphoric acid aqueous solution containing germanium to a substrate having a hafnium oxide film and a tantalum nitride film exposed on a surface thereof. A method according to an embodiment of the present invention includes the steps of: storing a phosphoric acid aqueous solution containing a ruthenium having a predetermined ruthenium concentration range in a tank; supplying an aqueous phosphoric acid solution in the tank to a nozzle, and applying an aqueous phosphoric acid solution from the nozzle a step of performing substrate processing by supplying the substrate to the substrate; a recovery step of recovering the phosphoric acid aqueous solution used for substrate processing from the nozzle to the substrate; and collecting the first aqueous phosphoric acid solution containing ruthenium at the first concentration a first phosphoric acid aqueous solution supply step supplied to the tank; a second phosphoric acid aqueous solution supply step of supplying a second aqueous phosphoric acid solution having a second concentration lower than the first concentration to the tank; and a predetermined supplementary start condition When it is satisfied, start the above first phosphate water soluble a liquid supply step and a start determination step of the second phosphoric acid aqueous solution supply step; and determining the first phosphoric acid aqueous solution in the first phosphoric acid aqueous solution supply step and the second phosphoric acid aqueous solution in the second phosphoric acid aqueous solution supply step The supply amount of the supply amount determines the step.

In this method, a substrate is treated with an aqueous phosphoric acid solution to selectively etch a tantalum nitride film exposed on the surface of the substrate. By controlling the concentration of ruthenium contained in the phosphoric acid aqueous solution to a predetermined ruthenium concentration range, etching of the ruthenium oxide film exposed on the surface of the substrate can be suppressed, whereby the selection ratio of the tantalum nitride film can be improved.

The aqueous phosphoric acid solution is supplied from the tank toward the nozzle and is supplied from the nozzle to the substrate. The used phosphoric acid aqueous solution used for the treatment of the substrate is recovered in the tank. When the predetermined supplementary start condition is satisfied, the first phosphoric acid aqueous solution containing ruthenium in the first concentration and the phosphoric acid aqueous solution containing ruthenium in the second concentration are supplied to the tank. By appropriately determining the supply amounts of the first and second phosphoric acid aqueous solutions, the concentration of the cesium phosphate in the tank can be controlled to a predetermined erbium concentration range.

Each of the first aqueous solution and the second aqueous phosphoric acid solution contains ruthenium in the first concentration and the second concentration, and the concentration values are each a fixed value, and need not be changed. This is because, by appropriately determining the respective supply amounts of the first and second phosphoric acid aqueous solutions, the first phosphoric acid aqueous solution, the second phosphoric acid aqueous solution, and the aqueous phosphoric acid solution in the tank are mixed, whereby the phosphoric acid aqueous solution having a predetermined concentration range can be obtained. Store in the tank. Therefore, the first aqueous phosphoric acid solution and the second aqueous phosphoric acid aqueous solution are prepared in advance, and when necessary, they are supplied to the tank only in a required amount, whereby the concentration of the phosphoric acid aqueous solution in the tank can be adjusted. Therefore, since the waiting time for adding the phosphoric acid aqueous solution to the tank can be reduced, the stable aqueous solution of phosphoric acid can be supplied to the substrate without impairing the productivity of the substrate treatment.

Furthermore, as long as it is prepared in advance, each of the first concentration and the second concentration includes Since the first and second aqueous phosphoric acid solutions may be used, it is not necessary to control the concentration of the first aqueous phosphoric acid solution and the second aqueous phosphoric acid solution. For example, a first- or second-concentration phosphoric acid aqueous solution can be prepared by quantitatively mixing a stock solution containing no hydrazine aqueous solution and a hydrazine concentrate containing hydrazine at a predetermined concentration. Of course, the concentration can be confirmed by the concentration meter in accordance with the need, but the concentration meter is not essential. Therefore, it is possible to supply a stable aqueous solution of phosphoric acid having a stable concentration to the substrate at a low cost.

In one embodiment of the present invention, the first concentration is a value within the predetermined enthalpy concentration range. According to this method, since the first concentration is a value within a predetermined erbium concentration range, the cesium concentration of the phosphoric acid aqueous solution in the tank can be easily guided to a value within a predetermined erbium concentration range by supplying the first phosphoric acid aqueous solution.

The first concentration may be a reference enthalpy concentration (the optimum erbium concentration value for substrate processing) within the predetermined erbium concentration range.

In one embodiment of the present invention, the second concentration is a value lower than the predetermined erbium concentration range. According to this method, since the second concentration is a value lower than the predetermined erbium concentration range, the cesium concentration of the phosphoric acid aqueous solution in the tank can be easily guided to a value within a predetermined erbium concentration range by supplying the second phosphoric acid aqueous solution. . In particular, when the substrate contains ruthenium, the phosphoric acid aqueous solution is supplied to the substrate, and the ruthenium of the substrate material is eluted into the phosphoric acid aqueous solution. Therefore, the concentration of the phosphoric acid aqueous solution recovered in the tank becomes higher than that supplied to the substrate. Before the higher. Here, by supplying the second phosphoric acid aqueous solution containing ruthenium in the second concentration lower than the predetermined ruthenium concentration range, the ruthenium concentration of the phosphoric acid aqueous solution in the tank can be easily guided to the predetermined ruthenium concentration range.

In an embodiment of the invention, the second concentration is zero. That is, in the present embodiment, the second phosphoric acid aqueous solution is an aqueous phosphoric acid solution containing no ruthenium. borrow By supplying such a second aqueous phosphoric acid solution to the tank, the rhodium concentration of the phosphoric acid aqueous solution in the tank can be easily guided to a predetermined rhodium concentration range.

In one embodiment of the present invention, in the supply amount determining step, the first and second phosphoric acid aqueous solutions are determined such that the concentration of rhodium in the phosphoric acid aqueous solution in the tank is adjusted to a predetermined reference rhodium concentration. Supply amount. According to this method, the first and second phosphoric acid aqueous solutions are supplied to the tank in an appropriately determined supply amount, whereby the first and second phosphoric acid aqueous solutions are mixed with the phosphoric acid aqueous solution recovered in the tank, and the tank can be mixed. The ruthenium concentration of the aqueous phosphoric acid solution is directed to the reference ruthenium concentration.

In the above-described supply amount determining step, the first and second phosphoric acid aqueous solutions are determined by setting the target value of the cerium concentration in the phosphoric acid aqueous solution in the tank to the first concentration. Supply amount.

In this method, the first concentration and the second phosphoric acid aqueous solution are determined by setting the first concentration as the adjustment target value, thereby mixing the first and second phosphoric acid aqueous solutions with the phosphoric acid aqueous solution recovered in the tank. The cesium concentration of the aqueous phosphoric acid solution in the tank was directed to the first concentration.

For example, when the first concentration is made equal to the reference enthalpy concentration, the cerium concentration of the phosphoric acid aqueous solution in the tank can be adjusted to the reference enthalpy concentration. In this case, when the aqueous phosphoric acid solution is first stored in the tank, only the first phosphoric acid aqueous solution may be supplied to the tank. Thereby, the phosphoric acid aqueous solution stored in the tank can be directly and quickly used for the treatment of the substrate without using a standby time for achieving uniformization of the concentration.

In one embodiment of the present invention, in the supply amount determining step, the supply amount of the first and second phosphoric acid aqueous solutions is determined based on the type of the substrate. The variation in the concentration of ruthenium in the aqueous phosphoric acid solution before and after the substrate treatment can be predicted based on the type of the substrate. Here, the first and second aqueous phosphoric acid solutions are determined based on the type of the substrate. The amount of supply can thereby appropriately adjust the ruthenium concentration of the aqueous phosphoric acid solution in the tank.

The type of the substrate refers to the material of the substrate, the type of the film formed on the surface of the substrate, the type of the pattern formed on the surface of the substrate, and other properties of the substrate which have an influence on the fluctuation of the germanium concentration before and after the use of the phosphoric acid aqueous solution.

In one embodiment of the present invention, in the supply amount determining step, the first and the first are determined based on the amount of cerium eluted from the substrate into the phosphoric acid aqueous solution by the phosphoric acid aqueous solution supplied from the nozzle. The amount of supply of 2 aqueous phosphoric acid solution. In the case where the substrate is eluted by treatment with an aqueous phosphoric acid solution, the amount of elution affects the concentration of rhodium in the recovered aqueous phosphoric acid solution. Here, the supply amount of the first and second phosphoric acid aqueous solutions is determined based on the amount of ruthenium eluted from the substrate, whereby the ruthenium concentration of the phosphoric acid aqueous solution in the tank can be appropriately adjusted.

In one embodiment of the present invention, in the supply amount determining step, the first and second phosphoric acid aqueous solutions are determined based on the recovery rate of the phosphoric acid aqueous solution recovered in the tank from the phosphoric acid aqueous solution supplied to the substrate from the nozzle. The amount of supply. Not all of the phosphoric acid aqueous solution discharged from the nozzle for processing the substrate is recovered to the tank, and is partially discarded, for example, with a rinsing treatment or the like. Here, the supply amount of the first and second phosphoric acid aqueous solutions is determined based on the recovery rate of the phosphoric acid aqueous solution, whereby the concentration of the phosphoric acid aqueous solution in the tank can be adjusted to a predetermined level while the required amount of the phosphoric acid aqueous solution is replenished to the tank. Concentration range.

In one embodiment of the present invention, in the supply amount determining step, the supply amount of the first and second phosphoric acid aqueous solutions is determined based on the number of substrates processed by the phosphoric acid aqueous solution supplied from the nozzle. . The greater the number of processed substrates, that is, the greater the number of times the phosphoric acid aqueous solution is used in the substrate treatment, the greater the concentration of ruthenium in the aqueous phosphoric acid solution in the bath is from the reference ruthenium concentration. Here, based on the processed base The amount of the first and second aqueous phosphoric acid solutions is determined by the number of sheets, whereby the concentration of the phosphoric acid aqueous solution in the tank can be appropriately adjusted.

The number of substrates to be processed refers to the number of substrates to be processed without adjustment of the germanium concentration by the supply of the first and second phosphoric acid aqueous solutions.

In an embodiment of the present invention, the supplementary start condition includes a liquid amount condition related to a liquid amount stored in the tank. In the present embodiment, the first and second phosphoric acid aqueous solutions are supplied as a trigger condition in accordance with the liquid amount condition relating to the amount of liquid stored in the tank. Specifically, the liquid amount can be reduced by reducing the amount of liquid in the tank to a predetermined lower limit liquid amount. Thereby, when the amount of liquid in the tank is reduced to the lower limit liquid amount, the first and second phosphoric acid aqueous solutions are replenished, and the rhodium concentration is adjusted.

In one embodiment of the present invention, the supplementary start condition includes a number of processing conditions relating to the number of substrates processed by the aqueous phosphoric acid solution supplied from the nozzle. In the present embodiment, the first and second phosphoric acid aqueous solutions are supplied under the condition that the number of processes relating to the number of substrates to be processed is used as a trigger condition. The greater the number of processed substrates, that is, the greater the number of times the phosphoric acid aqueous solution is used in the substrate treatment, the greater the concentration of ruthenium in the aqueous phosphoric acid solution in the bath is from the reference ruthenium concentration. Here, for example, when the number of processed sheets reaches a predetermined value, the first and second aqueous phosphoric acid solutions are supplied as trigger conditions, and the erbium concentration of the phosphoric acid aqueous solution in the tank is adjusted. Thereby, the substrate can be treated with a stable aqueous solution of phosphoric acid.

In one embodiment of the present invention, the supplementary start condition includes a erbium concentration condition relating to a ruthenium concentration in an aqueous phosphoric acid solution supplied from the groove toward the nozzle. In this method, the enthalpy concentration condition relating to the ruthenium concentration in the aqueous phosphoric acid solution supplied from the tank toward the nozzle is used as a trigger condition, and the first condition is supplied. And a second aqueous phosphoric acid solution. More specifically, when the ruthenium concentration in the phosphoric acid aqueous solution supplied to the substrate deviates from the reference value by a predetermined value or more, the first and second phosphoric acid aqueous solutions are supplied to the tank to adjust the ruthenium concentration. Thereby, the substrate can be treated with a stable aqueous solution of phosphoric acid.

In one embodiment of the present invention, the method further includes a substrate holding step of holding the substrate horizontally, and supplying the phosphoric acid aqueous solution from the nozzle to a surface of the substrate held in the substrate holding step. In this method, the substrate is held horizontal, and an aqueous phosphoric acid solution is supplied from the nozzle to the surface of the substrate. For example, one substrate is horizontally held by a substrate holder, and an aqueous phosphoric acid solution is discharged from a nozzle toward the surface of the substrate. Thus, in the so-called monolithic type process, it is important to accurately adjust the concentration of ruthenium in the aqueous phosphoric acid solution discharged from the nozzle. When the adjustment of the ruthenium concentration is insufficient, there is a problem that the processing quality is uneven between the plurality of substrates to be processed. In order to uniformize the substrate processing, it is preferable to perform a substrate rotation step of rotating the substrate held by the substrate holder in parallel when the phosphoric acid aqueous solution is supplied.

In one embodiment of the present invention, the method further includes a third aqueous phosphoric acid supply step of different from the first concentration and the second concentration. 3 A third aqueous solution of phosphoric acid containing rhodium is supplied to the above tank.

In this method, a third aqueous phosphoric acid solution containing ruthenium in the third concentration can be supplied to the tank. Thereby, the adjustment width of the ruthenium concentration in the aqueous phosphoric acid solution in the tank can be widened. The first aqueous phosphoric acid solution and the third aqueous phosphoric acid solution may be selectively used in combination with the type of the substrate.

In an embodiment of the present invention, the aqueous phosphoric acid solution is stored In the step of the above-described tank, the third aqueous phosphoric acid solution supply step is carried out. Further, the third concentration is higher than the first concentration. For example, when the aqueous phosphoric acid solution is first stored in the tank, the third aqueous phosphoric acid solution having a high cerium concentration may be supplied to the tank. Then, after the phosphoric acid aqueous solution having an increased ruthenium concentration due to the treatment of the substrate is recovered in the tank, when the ruthenium concentration in the phosphoric acid aqueous solution is adjusted, the first aqueous phosphoric acid solution having a low concentration may be supplied to the tank.

In one embodiment of the present invention, the tank includes a recovery tank into which a phosphoric acid aqueous solution used for substrate processing is introduced via a recovery pipe, and a supply tank that is supplied and stored via a mixing liquid supply pipe. The phosphoric acid aqueous solution in the recovery tank; the phosphoric acid aqueous solution stored in the supply tank is supplied to the nozzle through a supply pipe, and the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution are supplied to the recovery tank.

In this method, the treated aqueous phosphoric acid solution is guided to a recovery tank via a recovery pipe. Next, the first and second aqueous phosphoric acid solutions are supplied to a recovery tank, and the concentration of rhodium in the phosphoric acid aqueous solution is adjusted in the recovery tank. The phosphoric acid aqueous solution whose concentration has been adjusted is supplied from the mixing liquid supply pipe to the supply tank, and is supplied from the supply tank to the processing liquid nozzle. Therefore, the concentration of ruthenium in the aqueous phosphoric acid solution in the supply tank is not affected by the liquid recovery, and therefore is stable. Thereby, a more stable aqueous solution of phosphoric acid having a higher concentration can be supplied from the processing liquid nozzle to the substrate.

In an embodiment of the present invention, the plurality of recovery tanks are provided. Furthermore, the method further includes a collection destination selection step of selecting a recovery destination of the phosphoric acid aqueous solution recovered through the recovery pipe from the plurality of recovery tanks, and a supply destination selection step of the first The supply destination of the phosphoric acid aqueous solution and the second phosphoric acid aqueous solution is selected to be selected at the above-mentioned recovery destination a recovery tank selected in the step; and a supplementary source selection step of selecting a recovery tank not selected in the recovery tank selection step in the plurality of recovery tanks as a phosphate for supplying the piping via the conditioning liquid The aqueous solution is replenished to a supplemental source of the above supply tank.

In this method, the used phosphoric acid aqueous solution is recovered to a recovery tank selected from a plurality of recovery tanks, and the phosphoric acid aqueous solution whose concentration has been adjusted is supplied from the unselected recovery tank to the supply tank. Thereby, the phosphoric acid aqueous solution can be replenished to the supply tank without stagnation, so that the supply of the phosphoric acid aqueous solution to the substrate does not stagnate. Thereby, the productivity of the substrate processing can be improved. Further, in the recovery tank used for the recovery of the aqueous phosphoric acid solution, the concentration of the ruthenium was adjusted by the supply of the first and second aqueous phosphoric acid solutions. Therefore, the concentration of ruthenium in the aqueous phosphoric acid solution supplied to the recovery tank of the supply tank is stabilized, so that the ruthenium concentration in the phosphoric acid aqueous solution of the supply tank can be stably maintained. Thereby, the concentration of ruthenium in the aqueous phosphoric acid solution used for the substrate treatment is more stable.

In one embodiment of the present invention, the method further includes the step of managing the supply amount of the first phosphoric acid aqueous solution in the first phosphoric acid aqueous solution supply step using the first integrated flowmeter; and using the second integrated calculation The flow meter manages the supply amount of the second aqueous phosphoric acid solution in the second phosphoric acid aqueous solution supply step.

In this method, the supply amount of the first and second phosphoric acid aqueous solutions can be accurately managed by using the integrated flow meter. Thereby, the concentration of ruthenium in the aqueous phosphoric acid solution in the tank can be accurately adjusted.

An embodiment of the present invention further provides a substrate processing apparatus suitable for performing the substrate processing method as described above. Substrate according to an embodiment of the present invention The processing apparatus includes: a substrate holding means that holds a substrate on which a ruthenium oxide film and a tantalum nitride film are exposed; and a nozzle that supplies a phosphoric acid aqueous solution containing ruthenium to the substrate held by the substrate holding means; And supplying a phosphoric acid aqueous solution containing a ruthenium having a predetermined ruthenium concentration range to the nozzle; and collecting a pipe for recovering the phosphoric acid aqueous solution used for the substrate treatment from the nozzle to the substrate; The phosphoric acid aqueous solution supply means supplies the first phosphoric acid aqueous solution containing ruthenium in the first concentration to the tank, and the second phosphoric acid aqueous solution supply means includes the second concentration having a bismuth at the second concentration lower than the first concentration a phosphoric acid aqueous solution is supplied to the tank; and a control means performs a phosphoric acid aqueous solution supply step and a supply amount determining step; and the phosphoric acid aqueous solution supply step controls the first aqueous phosphoric acid aqueous solution supply means when a predetermined supplementary start condition is satisfied The second phosphoric acid aqueous solution supply means supplies the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution to the above ; The line feeding amount determination step determines the supply amount of the second aqueous solution of a phosphoric acid.

In one embodiment of the present invention, the control means is the amount of ruthenium eluted from the substrate to the phosphoric acid aqueous solution by the type of the substrate and the phosphoric acid aqueous solution supplied from the nozzle in the supply amount determining step. At least one of a recovery rate of the phosphoric acid aqueous solution recovered into the tank from the phosphoric acid aqueous solution supplied to the substrate from the nozzle, and a number of substrates processed by the phosphoric acid aqueous solution supplied from the nozzle The amount of supply of the first aqueous phosphoric acid solution and the second aqueous phosphoric acid solution is determined.

In one embodiment of the present invention, the supplementary condition includes a liquid amount condition relating to a liquid amount stored in the tank, and a number of substrates processed by the phosphoric acid aqueous solution supplied from the nozzle. The number of treatment conditions and the enthalpy concentration in the aqueous phosphoric acid solution supplied from the tank toward the nozzle At least one of the concentration conditions.

In one embodiment of the present invention, the substrate processing apparatus further includes a third aqueous phosphoric acid solution supply means, wherein the third aqueous phosphoric acid aqueous solution supply means is different from any of the first concentration and the second concentration The third concentration includes a third aqueous phosphoric acid solution containing ruthenium supplied to the tank, and the control means further controls the third aqueous phosphoric acid solution supply means.

In one embodiment of the present invention, the tank includes a recovery tank into which a phosphoric acid aqueous solution used for substrate processing is introduced via a recovery pipe, and a supply tank that is supplied via a mixing liquid supply pipe. The phosphoric acid aqueous solution stored in the recovery tank; the phosphoric acid aqueous solution stored in the supply tank is supplied to the nozzle through a supply pipe, and the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution are supplied to the recovery tank.

In an embodiment of the present invention, the plurality of recovery tanks are provided. Further, the control means further performs the following steps: a recovery destination selection step of selecting a recovery destination of the phosphoric acid aqueous solution recovered through the recovery pipe from the plurality of recovery tanks; and a supply destination selection step The supply destination of the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution is selected as a recovery tank selected in the collection destination selection step; and a supplementary source selection step is selected in the plurality of recovery tanks for the recovery The recovery tank not selected in the tank selection step serves as a supplementary source for replenishing the phosphoric acid aqueous solution to the supply tank via the mixing liquid supply piping.

In one embodiment of the present invention, the substrate processing apparatus further includes: a first integrated flowmeter that measures a supply amount of the first phosphoric acid aqueous solution supplied to the tank by the first phosphoric acid aqueous solution supply means; and a second Accumulating flowmeter, Measuring the supply amount of the second phosphoric acid aqueous solution supplied to the tank by the second aqueous phosphoric acid solution supply means; and the control means further performing a supply amount management step based on the first integrated flowmeter and the first (2) The measurement results of the flowmeter are integrated, and the supply of the first aqueous phosphoric acid solution and the second aqueous phosphoric acid solution to the tank is managed.

The above and other objects, features and advantages of the present invention will become apparent from

1‧‧‧Substrate processing unit

2‧‧‧Processing unit

3‧‧‧Control device

3a‧‧‧ computer body

3b‧‧‧ peripheral devices

4‧‧‧ chamber

5‧‧‧Rotary chuck

6‧‧‧Chuck pin

7‧‧‧Spinning base

8‧‧‧Rotary axis

9‧‧‧Rotary motor

10‧‧‧Processing Cup

11‧‧‧Baffle

11a‧‧‧Top Board

11b‧‧‧Cylinder

12‧‧‧ cup

12a‧‧‧Liquid

13‧‧‧Baffle lifting unit

14‧‧‧phosphoric acid nozzle

15‧‧‧phosphoric acid piping

16‧‧‧Phosphate valve

17‧‧‧1st Nozzle Moving Unit

18‧‧‧SC1 nozzle

19‧‧‧SC1 piping

20‧‧‧SC1 valve

21‧‧‧2nd Nozzle Moving Unit

22‧‧‧Eluent nozzle

23‧‧‧Eluent piping

24‧‧‧Eluent valve

29‧‧‧Valves

30‧‧‧phosphoric acid supply system

31‧‧‧Supply tank

32‧‧‧Recycling piping

33‧‧‧ pump

34‧‧‧heater

35‧‧‧Filter

36‧‧‧Differential piping

37‧‧‧矽 concentration meter

38‧‧‧Valves

39‧‧‧Valves

40‧‧‧Drainage system

41‧‧‧Drainage piping

42‧‧‧Drain valve

43‧‧‧Drainage flow adjustment valve

44‧‧‧Liquid sensor

44h‧‧‧Upper limit sensor

44L‧‧‧lower limit sensor

44t‧‧‧target sensor

45A‧‧‧1st emission system

45B‧‧‧2nd emission system

46A‧‧‧Emission piping

46B‧‧‧Drainage piping

47A‧‧‧Drain valve

47B‧‧‧Drain valve

50‧‧‧New Liquid Replenishment System

51‧‧‧New liquid mixing tank

52‧‧‧New liquid replenishing piping

52A‧‧‧1st tube

52B‧‧‧2nd tube

53‧‧‧New fluid supplement valve

53A‧‧‧1st new liquid filling valve

53B‧‧‧2nd new liquid filling valve

54‧‧‧ pump

55‧‧‧phosphoric acid piping

56‧‧‧phosphoric acid solution valve

57‧‧‧矽Concentrate piping

58‧‧‧矽 valve

59‧‧‧ Phosphate stock supplement pipe

59A‧‧‧1st pipe

59B‧‧‧2nd tube

60‧‧‧phosphoric acid supplement valve

60A‧‧‧1st Phosphate Solution Filling Valve

60B‧‧‧2nd Phosphate Solution Filling Valve

61‧‧‧ accumulating flowmeter

62‧‧‧Integrated flowmeter

63‧‧‧Circular path

64‧‧‧ valve

65‧‧‧ valve

70‧‧‧Recycling system

71‧‧‧Recycling piping

71A‧‧‧1st recycling branch

71B‧‧‧2nd recycling branch

72‧‧‧Recovery valve

72A‧‧‧1st recovery valve

72B‧‧‧2nd recovery valve

75A, 75B‧‧‧Limited liquid volume sensor

76A, 76B‧‧‧Recycling stop volume sensor

77A, 77B‧‧‧ Target Liquid Sensor

80‧‧‧Draining system

81‧‧‧Draining piping

82‧‧‧Drain valve

90A‧‧‧1st recycling tank

90B‧‧‧2nd recycling tank

91‧‧‧Processor

92‧‧‧Main storage device

93‧‧‧Auxiliary storage device

94‧‧‧Reading device

95‧‧‧Communication devices

96‧‧‧ Input device

97‧‧‧ display device

100‧‧‧Supply piping

100A‧‧‧1st pipe

100B‧‧‧2nd tube

101A‧‧‧1st supplementary valve

101B‧‧‧2nd supplementary valve

102‧‧‧ pump

103‧‧‧heater

111‧‧‧2nd new liquid mixing tank

112‧‧‧2nd phosphate stock solution valve

113‧‧‧2nd phosphate stock solution piping

114‧‧‧2nd valve

115‧‧‧Second-phase concentrate piping

121‧‧‧1st new liquid supplement source selection valve

122‧‧‧2nd new liquid supplement source selection valve

A1‧‧‧Rotation axis

Fn‧‧‧ nitride film

Fo‧‧‧Oxide film

HC‧‧‧ main computer

M‧‧‧Removable Media

P‧‧‧ program

R‧‧‧ Formula

W‧‧‧Substrate

S1-S9, S11-S20, S21-S25, S31-S33, S41-S49‧‧

Fig. 1 is a schematic view showing a processing unit provided in a substrate processing apparatus according to an embodiment of the present invention as seen from a horizontal direction.

FIG. 2 is a schematic view for explaining a configuration of a phosphoric acid supply system provided in the substrate processing apparatus.

Fig. 3 is a block diagram for explaining a main electrical configuration of the substrate processing apparatus.

4 is a cross-sectional view showing an example of a substrate processed by the substrate processing apparatus.

Fig. 5 is a step diagram for explaining an example of substrate processing performed by the substrate processing apparatus.

Fig. 6 is a flow chart for explaining processing associated with supply of an aqueous phosphoric acid solution in the above substrate processing apparatus.

Fig. 7 is a schematic view showing the configuration of a substrate processing apparatus according to another embodiment of the present invention, and mainly shows a configuration of a phosphoric acid supply system.

Fig. 8 is a block diagram for explaining an electrical configuration of a substrate processing apparatus having the configuration of Fig. 7;

FIG. 9 is a flow chart for explaining a process related to supply of an aqueous phosphoric acid solution in the substrate processing apparatus of the configuration of FIG. 7, and shows an operation related to supply of a phosphoric acid aqueous solution to the substrate and supply of a phosphoric acid aqueous solution to the supply tank.

Fig. 10 is a flow chart for explaining the process associated with the supply of the phosphoric acid aqueous solution in the substrate processing apparatus of the configuration of Fig. 7, and shows the recovery destination of the selected phosphoric acid and the source of the phosphoric acid aqueous solution selected for the supply tank. Related actions.

Fig. 11 is a flow chart for explaining the process associated with the supply of the phosphoric acid aqueous solution in the substrate processing apparatus of the configuration of Fig. 7, and shows the operation related to the replenishment of the new liquid to the recovery tank.

Fig. 12 is a schematic view showing the configuration of a substrate processing apparatus according to still another embodiment of the present invention.

Fig. 1 is a schematic view showing a processing unit provided in a substrate processing apparatus according to an embodiment of the present invention as seen from a horizontal direction. The substrate processing apparatus 1 is a one-piece apparatus for processing a substrate W such as a semiconductor wafer one by one. The substrate processing apparatus 1 includes a plurality of processing units 2 (only one is shown in FIG. 1) for processing the substrate W by a processing fluid such as a processing liquid or a processing gas, and a transfer robot that transports the substrate W to the plurality of processing units 2 ( Not shown) and the control device 3 (control means) for controlling the substrate processing apparatus 1.

The processing unit 2 includes a rotary chuck 5 that horizontally holds the substrate W in the chamber 4 and rotates around a vertical rotation axis A1 passing through the central portion of the substrate W; and a cylindrical processing cup 10 that receives The treatment liquid scattered from the substrate W toward the outside.

The rotary chuck 5 includes a disc-shaped rotating base 7 which is water The flat posture is held; a plurality of collet pins 6 that hold the substrate W in a horizontal position above the spin base 7; a rotating shaft 8 that extends downward from a central portion of the spin base 7; and a rotary motor 9 The rotation base 8 and the plurality of chuck pins 6 are rotated by rotating the rotary shaft 8. The rotary chuck 5 is not limited to a clamp type chuck in which a plurality of chuck pins 6 are brought into contact with the outer peripheral surface of the substrate W, and may be a back surface (lower surface of the substrate W) by forming a non-element forming surface. A vacuum suction type chuck that is adsorbed on the upper surface of the spin base 7 to horizontally hold the substrate W.

The processing cup 10 includes a plurality of baffles 11 that receive liquid discharged from the substrate W toward the outside, and a plurality of cups 12 that receive the liquid guided downward by the baffle 11. The baffle 11 includes a cylindrical tubular portion 11b that surrounds the rotary chuck 5, and an annular top plate portion 11a that extends obliquely upward from the upper end portion of the tubular portion 11b toward the rotation axis A1. The plurality of top plate portions 11a are overlapped in the vertical direction, and the plurality of cylindrical portions 11b are arranged in a concentric cylindrical shape. A plurality of cups 12 are disposed below the plurality of cylindrical portions 11b, respectively. The cup 12 is formed with an annular receiving groove 12a that is open upward.

The processing unit 2 includes a baffle lifting unit 13 that individually raises and lowers a plurality of baffles 11. The shutter lifting unit 13 moves the shutter 11 up and down in the vertical direction between the upper position and the lower position. In the upper position, the upper end of the baffle 11 is located above the substrate holding position of the substrate W by the rotary chuck 5. In the lower position, the upper end of the baffle 11 is located further below the substrate holding position. The upper end of the annular portion of the top plate portion 11a corresponds to the upper end of the baffle 11. The upper end of the baffle 11 surrounds the substrate W and the spin base 7 in a plan view.

In a state where the substrate W is rotated by the rotary chuck 5, when the processing liquid is supplied to the substrate W, the processing liquid supplied to the substrate W is directed to the base by centrifugal force. The board W is opened around. When the processing liquid is supplied to the substrate W, at least one upper end of the baffle 11 is disposed above the substrate W. Therefore, the treatment liquid such as the chemical liquid or the eluent discharged to the periphery of the substrate W is received by any of the baffles 11, and is guided to the cup 12 corresponding to the baffle 11.

The processing unit 2 includes a phosphoric acid nozzle 14 that discharges an aqueous phosphoric acid solution downward toward the upper surface of the substrate W. The phosphoric acid nozzle 14 is connected to a phosphate pipe 15 that guides an aqueous phosphoric acid solution. When the phosphate valve 16 disposed in the phosphoric acid pipe 15 is opened, the phosphoric acid aqueous solution is continuously discharged downward from the discharge port of the phosphoric acid nozzle 14.

The aqueous phosphoric acid solution is an aqueous solution containing phosphoric acid (H ₃ PO ₄ ) as a main component. The concentration of the phosphoric acid in the aqueous phosphoric acid solution is, for example, in the range of 50% to 100%, preferably about 90%. The boiling point of the aqueous phosphoric acid solution differs depending on the concentration of phosphoric acid in the aqueous phosphoric acid solution, and is approximately in the range of 140 ° C to 195 ° C. The aqueous phosphoric acid solution discharged from the phosphoric acid nozzle 14 contains ruthenium. The concentration of rhodium in the aqueous phosphoric acid solution is controlled to a specified concentration range. The cerium concentration range is, for example, 15 ppm to 150 ppm, preferably 40 ppm to 60 ppm. The lanthanide contained in the aqueous phosphoric acid solution may be a ruthenium monomer, a ruthenium compound, or both. Further, the ruthenium contained in the phosphoric acid aqueous solution may be a ruthenium which is eluted from the substrate W by the supply of the phosphoric acid aqueous solution. Further, the ruthenium added to the phosphoric acid aqueous solution may be contained in the ruthenium phosphate aqueous solution.

Although not shown in the drawings, the phosphate valve 16 includes a valve body that forms a flow path, a valve body that is disposed in the flow path, and an actuator that moves the valve body. The same is true for the other valves described below. The actuator may be a pneumatic actuator, may be an electric actuator, or may be an actuator other than the actuator. The control device 3 opens and closes the phosphate valve 16 by controlling the actuator, or changes the opening degree thereof.

In the present embodiment, the phosphoric acid nozzle 14 is provided in the chamber 4 The shape of the scanning nozzle that moves. The phosphoric acid nozzle 14 is coupled to the first nozzle moving unit 17, and the first nozzle moving unit 17 moves the phosphoric acid nozzle 14 in at least one of the vertical direction and the horizontal direction. The first nozzle moving unit 17 is a processing position at which the phosphoric acid nozzle 14 is immersed in the upper surface of the substrate W by the phosphoric acid aqueous solution discharged from the phosphoric acid nozzle 14 and the retreating of the phosphoric acid nozzle 14 on the outer side of the rotary chuck 5 in plan view. Move between positions.

The processing unit 2 includes an SC1 nozzle 18 that discharges SC1 (containing a mixed liquid of NH ₄ OH and H ₂ O ₂ ) downward toward the upper surface of the substrate W. The SC1 nozzle 18 is connected to the SC1 pipe 19 of the pilot SC1. When the SC1 valve 20 interposed in the SC1 pipe 19 is opened, the SC1 is continuously discharged from the discharge port of the SC1 nozzle 18.

In the present embodiment, the SC1 nozzle 18 has a form of a scanning nozzle that can move in the chamber 4. The SC1 nozzle 18 is coupled to the second nozzle moving unit 21. The second nozzle moving unit 21 moves the SC1 nozzle 18 in at least one of the vertical direction and the horizontal direction. The second nozzle moving unit 21 is a processing position at which the SC1 nozzle 18 is liquided from the SC1 discharged from the SC1 nozzle 18 to the upper surface of the substrate W, and the retracted position of the SC1 nozzle 18 on the outer side of the rotary chuck 5 in a plan view. Move between.

The processing unit 2 further includes an eluent nozzle 22 that discharges the eluent toward the upper surface of the substrate W. The eluent nozzle 22 is connected to the eluent pipe 23 that guides the eluent. When the eluent valve 24 interposed in the eluent pipe 23 is opened, the eluent is continuously discharged downward from the discharge port of the eluent nozzle 22. The eluent is, for example, pure water (deionized water). Other examples of the eluent are electrolytic ionized water, hydrogen water, ozone water, hydrochloric acid water having a diluted concentration (for example, about 10 ppm to 100 ppm).

In the present embodiment, the eluent nozzle 22 is a fixed nozzle that discharges the eluent from the discharge port where the position is fixed. The eluent nozzle 22 is fixed relative to the bottom of the chamber 4. The processing unit 2 may further include a nozzle moving unit that causes the eluent nozzle 22 to immerse the eluent discharged from the eluent nozzle 22 to a processing position on the upper surface of the substrate W, and The eluent nozzle 22 moves between the retracted positions on the outer side of the reversing chuck 5 in a plan view.

FIG. 2 is a schematic view for explaining the configuration of the phosphoric acid supply system 30 provided in the substrate processing apparatus 1.

The phosphoric acid supply system 30 includes a supply tank 31 (tank) for storing the phosphoric acid aqueous solution discharged from the phosphoric acid nozzle 14 and a circulation pipe 32 for circulating the phosphoric acid aqueous solution in the supply tank 31. The phosphoric acid supply system 30 further includes a pump 33 that transports the phosphoric acid aqueous solution in the supply tank 31 to the circulation pipe 32, and a heater 34 that heats on the way of the circulation path formed by the supply tank 31 and the circulation pipe 32. An aqueous phosphoric acid solution; and a filter 35 for removing foreign matter from an aqueous phosphoric acid solution flowing in the circulation pipe 32. The pump 33, the filter 35, and the heater 34 are interposed in the circulation pipe 32. The supply tank 31 is an example of a tank for storing an aqueous phosphoric acid solution.

The phosphate pipe 15 as a supply pipe for supplying the phosphoric acid aqueous solution to the phosphoric acid nozzle 14 is connected to the circulation pipe 32. The pump 33 continuously supplies the aqueous phosphoric acid solution in the supply tank 31 to the circulation pipe 32. The phosphoric acid supply system 30 may be provided with a pressurizing device instead of the pump 33, and the pressurizing device pushes the aqueous phosphoric acid solution in the supply tank 31 to the circulation pipe 32 by raising the gas pressure in the supply tank 31. Each of the pump 33 and the pressurizing device is an example of a liquid feeding device that sends the aqueous phosphoric acid solution in the supply tank 31 to the circulation pipe 32 and the phosphoric acid pipe 15.

The upstream end and the downstream end of the circulation pipe 32 are connected to the supply tank 31. The aqueous phosphoric acid solution is sent from the supply tank 31 to the upstream end of the circulation pipe 32, and returns to the supply tank 31 from the downstream end of the circulation pipe 32. Thereby, the aqueous phosphoric acid solution in the supply tank 31 is circulated through the circulation path. During the cycle, the foreign matter contained in the phosphoric acid aqueous solution is removed by the filter 35, and the phosphoric acid aqueous solution is heated by the heater 34. Thereby, the aqueous phosphoric acid solution in the supply tank 31 is maintained at a fixed temperature higher than room temperature (for example, 5 ° C to 30 ° C). The temperature of the aqueous phosphoric acid solution heated by the heater 34 may be the boiling point of the concentration (phosphoric acid concentration) of the aqueous phosphoric acid solution, or may be a temperature lower than the boiling point.

A branch pipe 36 is connected to the circulation pipe 32. A helium concentration meter 37 is disposed in the middle of the branch pipe 36, and the branch pipe 36 is branched from the circulation pipe 32 to pass through the helium concentration meter 37, and then merges to the circulation pipe 32. In the branch pipe 36, valves 38 and 39 are respectively disposed on both sides of the upstream side and the downstream side of the helium concentration meter 37.

In order to discharge the phosphoric acid aqueous solution in the supply tank 31, an exhaust system 40 is provided. The discharge system 40 includes a discharge pipe 41 that discharges the phosphoric acid aqueous solution in the supply tank 31, and a discharge valve 42 that is disposed in the discharge pipe 41. The discharge pipe 41 may also be provided with a discharge flow rate adjustment valve 43 for adjusting the discharge flow rate of the phosphoric acid aqueous solution. When the discharge valve 42 is opened, the phosphoric acid aqueous solution in the supply tank 31 is discharged to the discharge pipe 41. Thereby, the amount of the phosphoric acid aqueous solution in the supply tank 31 can be reduced as needed, or all of the phosphoric acid aqueous solution in the supply tank 31 can be drained.

In order to detect the amount of the phosphoric acid aqueous solution in the supply tank 31, a plurality of liquid amount sensors 44 are provided. The plurality of liquid amount sensors 44 include an upper limit sensor 44h, a lower limit sensor 44L, and a target sensor 44t. The upper limit sensor 44h detects whether or not the liquid amount of the phosphoric acid aqueous solution in the supply tank 31 is equal to or greater than the upper limit of the predetermined liquid amount range. The lower limit sensor 44L is the amount of the phosphoric acid aqueous solution in the supply tank 31 Whether it is detected below the lower limit of the specified liquid amount range. The target sensor 44t detects whether or not the liquid amount of the phosphoric acid aqueous solution in the supply tank 31 is equal to or higher than a target value between the upper limit value and the lower limit value. When the amount of the phosphoric acid aqueous solution in the supply tank 31 is reduced to the lower limit by the use of the phosphoric acid aqueous solution, the unused aqueous phosphoric acid solution (new liquid) is replenished from the new liquid replenishing system 50. The new liquid system is replenished until the liquid amount of the phosphoric acid aqueous solution in the supply tank 31 reaches the target value.

The new liquid replenishing system 50 includes: a new liquid mixing tank 51; a new liquid replenishing pipe 52 that guides the unused phosphoric acid aqueous solution from the new liquid mixing tank 51 toward the supply tank 31; the new liquid replenishing valve 53 is provided The new liquid replenishing pipe 52; and the pump 54 are similarly disposed in the new liquid replenishing pipe 52. The stock solution of the phosphoric acid aqueous solution (hereinafter referred to as "phosphoric acid stock solution") is supplied to the new liquid mixing tank 51 via the phosphate raw material piping 55. The phosphoric acid stock solution means an aqueous phosphoric acid solution to which no rhodium is added. A phosphate raw liquid valve 56 that opens and closes the flow path is interposed in the phosphate raw material pipe 55. Further, the hydrazine concentrate is supplied to the new liquid mixing tank 51 via the hydrazine concentrate piping 57. The weir concentrate pipe 57 is provided with a weir valve 58 that opens and closes the flow path. The new liquid replenishing system 50 further includes a phosphate raw material replenishing pipe 59 for supplying the phosphoric acid raw material to the supply tank 31. The phosphate raw material supply pipe 59 is branched from the phosphoric acid raw material pipe 55 on the upstream side of the phosphoric acid raw material valve 56, and is connected to the supply tank 31 without passing through the new liquid mixing tank 51. A phosphate stock solution replenishing valve 60 that opens and closes the flow path is provided in the middle of the phosphate raw material replenishing pipe 59.

The new liquid replenishing pipe 52 and the phosphoric acid raw material replenishing pipe 59 are provided with integrated flow meters 61 and 62, respectively.

The phosphate stock solution valve 56 is opened to supply a fixed amount of the phosphoric acid stock solution to the new liquid mixing tank 51, and the helium valve 58 is opened to supply a fixed amount of the cerium concentrate to the new liquid mixing tank 51, thereby mixing the phosphate stock solution at a predetermined ratio. With hydrazine concentrate. In other words, The phosphoric acid stock solution and the hydrazine concentrate are supplied to the new liquid mixing tank 51 in a quantitative manner so as to have a predetermined supply ratio. Thereby, a phosphoric acid aqueous solution containing a ruthenium concentration (for example, 50 ppm, a first concentration) is prepared in the fresh liquid mixing tank 51.

The ruthenium concentration of the phosphoric acid aqueous solution prepared in the fresh liquid mixing tank 51 is not necessarily confirmed, but a circulation path 63 that is circulated by the krypton concentration meter 37 may be provided, and the ruthenium concentration may be confirmed as needed. In the circulation path 63, valves 64 and 65 are interposed on the upstream side and the downstream side of the helium concentration meter 37, respectively.

By opening the new liquid replenishing valve 53, the pump 54 is driven, and the new liquid (the unused phosphoric acid aqueous solution containing the crucible at the reference crucible concentration) which is blended in the new liquid mixing tank 51 can be replenished to the supply tank 31. This supplemental amount can be measured by the integrated flow meter 61. Further, by opening the phosphoric acid stock replenishing valve 60, the phosphate stock solution (unused phosphoric acid aqueous solution containing no antimony) can be replenished to the supply tank 31. This supplemental amount can be measured by the integrated flow meter 62. The concentration of ruthenium in the phosphate stock solution is zero (one example of the second concentration).

The new liquid preparation tank 51, the new liquid supply pipe 52, the new liquid supply valve 53, the pump 54, and the like constitute a first aqueous phosphoric acid solution for supplying a phosphoric acid aqueous solution (first aqueous phosphoric acid solution) having a standard hydrazine concentration (example of the first concentration). Supply means. In addition, the phosphoric acid stock solution replenishing pipe 59 and the phosphoric acid stock solution replenishing valve 60 and the like constitute a second phosphoric acid aqueous solution supply means for supplying a phosphoric acid aqueous solution (second aqueous phosphoric acid solution) having a zero concentration (in the second concentration).

The substrate processing apparatus 1 further includes a recovery system 70 for recovering the used phosphoric acid aqueous solution used in the processing of the substrate W. The recovery system 70 includes a processing cup 10, a recovery pipe 71, and a recovery valve 72. The recovery pipe 71 is guided to the supply tank 31 by the aqueous phosphoric acid solution received by the processing cup 10. The recovery valve 72 opens and closes the flow path of the recovery pipe 71.

The substrate processing apparatus 1 further includes: a liquid discharge system 80, which is used The treatment liquid used for the treatment using the substrate W is discarded. The liquid discharge system 80 includes a liquid discharge pipe 81 connected to the processing cup 10 or the recovery pipe 71, and a liquid discharge valve 82 that opens and closes the flow path of the liquid discharge pipe 81.

When the recovery valve 72 is opened and the drain valve 82 is closed, the aqueous phosphoric acid solution received by the treatment cup 10 is recovered into the supply tank 31 by the recovery pipe 71. When the used treatment liquid is discarded, the discharge valve 72 is closed and the discharge valve 82 is opened. Thereby, the other treatment liquid of the phosphoric acid aqueous solution received by the processing cup 10 is discharged to the liquid discharge pipe 81.

FIG. 3 is a block diagram for explaining a main electrical configuration of the substrate processing apparatus 1. The control device 3 includes a computer main body 3a and a peripheral device 3b connected to the computer main body 3a. The computer main body 3a includes a processor (CPU, Central Processing Unit) 91 and a main storage device 92. The peripheral device 3b includes a program P that is executed by the processor 91, an auxiliary storage device 93 that stores various materials, and a reading device 94 that reads information from the removable media M (Removable Media); The communication device 95 communicates with an external device such as the host computer HC.

An input device 96 and a display device 97 are connected to the control device 3. The input device 96 is a device that is operated by an operator such as a user or a maintenance person in charge to input information to the substrate processing apparatus 1. The display device 97 displays various kinds of information on the display screen and provides them to the operator or the like. The input device 96 can also be a keyboard, a pointing device, a touch panel, or the like.

The processor 91 executes the program P stored in the auxiliary storage device 93. The program P in the auxiliary storage device 93 can also be pre-installed in the control device 3. In addition, the program P can also be imported from the removable medium M into the auxiliary storage device 93 by the reading device 94. In addition, the program P can also be autonomous computer HC via the communication device 95. Other external devices are acquired and imported into the auxiliary storage device.

The auxiliary storage device 93 and the removable medium M are non-volatile memories that retain memory even if power is not supplied. The auxiliary storage device 93 can also be, for example, a magnetic storage device such as a hard disk. The removable medium M can also be a compact disc or a semiconductor memory. The auxiliary storage device 93 and the removable medium M are examples of a computer-readable recording medium on which the program P is recorded.

The control device 3 controls the substrate processing apparatus 1 such that the substrate W is processed in accordance with the recipe R specified by the host computer HC. In particular, the control device 3 controls each part of the processing unit 2 and the phosphoric acid supply system 30. More specifically, the control device 3 controls the rotary motor 9, the shutter lift unit 13, the nozzle moving units 17, 21, the valves 16, 20, 24, and the like. Further, the control device 3 controls the pumps 33, 54, the heater 34, the valves 38, 39, 42, 53, 56, 58, 60, 64, 65, 72 and the like. Further, a signal from the sensor type is input to the control device 3. The sensor type includes a liquid amount sensor 44, a helium concentration meter 37, and an integrated flow meter 61, 62.

The auxiliary storage device 93 stores a plurality of recipes R. The formulation R contains information on the processing contents, processing conditions, and processing procedures of the predetermined substrate W. At least one of the processing contents, processing conditions, and processing procedures of the plurality of recipes R-based substrates W is different. The steps of the substrate processing are realized by the control device 3 controlling the substrate processing device 1 with the recipe R. That is, the control device 3 is programmed to perform the steps of the substrate processing.

4 is a cross-sectional view showing an example of a substrate W processed by the substrate processing apparatus 1. The substrate W has a tantalum wafer having a surface (element forming surface) on which the tantalum oxide film Fo and the tantalum nitride film Fn are exposed. In an example of substrate processing to be described later, a phosphoric acid aqueous solution containing ruthenium is supplied to such a substrate W, whereby the tantalum nitride film Fn is performed. Select the etch. In other words, the tantalum nitride film Fn can be etched at a predetermined etching rate (etching amount per unit time) while suppressing etching of the ruthenium oxide film Fo.

FIG. 5 is a step diagram for explaining an example of substrate processing performed by the substrate processing apparatus 1. The substrate W to be processed is carried into the chamber 4 by the transfer robot, and is transferred to the rotary chuck 5 (step S1). After the transfer robot is retracted to the outside of the chamber 4, the control device 3 rotates the rotary chuck 5, thereby rotating the substrate W about the vertical rotation axis A1 (step S2).

In this state, a phosphoric acid aqueous solution is supplied to the substrate W (step S3). More specifically, the first nozzle moving unit 17 moves the phosphoric acid nozzle 14 to the processing position, and the shutter raising unit 13 causes any of the shutters 11 to face the substrate W. Thereafter, the phosphoric acid valve 16 is opened, and the phosphoric acid aqueous solution is discharged from the phosphoric acid nozzle 14. When the phosphoric acid nozzle 14 discharges the phosphoric acid aqueous solution, the first nozzle moving unit 17 may be a central processing position in which the phosphoric acid nozzle 14 is immersed in the phosphoric acid aqueous solution discharged from the phosphoric acid nozzle 14 to the central portion of the upper surface of the substrate W, and The aqueous phosphoric acid solution discharged from the phosphoric acid nozzle 14 is moved to the outer peripheral processing position of the peripheral portion of the upper surface of the substrate W. Further, the phosphoric acid nozzle 14 may be made stationary so that the position of the phosphoric acid aqueous solution is located at the central portion of the upper surface of the substrate W.

The aqueous phosphoric acid solution discharged from the phosphoric acid nozzle 14 is applied to the upper surface of the substrate W, and then flows outward along the upper surface of the substrate W that is rotated. Thereby, a liquid film of a phosphoric acid aqueous solution covering the entire upper surface of the substrate W is formed, and an aqueous phosphoric acid solution is supplied to the entire upper surface of the substrate W. It is uniformly supplied to the entire area of the upper surface of the substrate W. Thereby, the upper surface of the substrate W is uniformly processed. When the phosphoric acid valve 16 is turned on and the predetermined time elapses, the phosphate valve 16 is closed to stop the discharge of the phosphoric acid aqueous solution from the phosphate valve 16. Thereafter, the first nozzle moving unit 17 is made to phosphoric acid The valve 16 is moved to the retracted position.

The phosphoric acid aqueous solution flies out to the outside of the substrate W by centrifugal force, and is received by the baffle 11 opposed to the substrate W. The phosphoric acid aqueous solution is further guided to the corresponding cup 12 by the baffle 11, and flows into the recovery pipe 71 and is recovered in the supply tank 31.

Next, a first eluent supply step of supplying pure water, which is one example of the eluent, to the upper surface of the substrate W is performed (step S4). Specifically, the eluent valve is opened 24, and the eluent nozzle 22 begins to spout pure water. The pure water that has been liquided to the upper surface of the substrate W flows outward along the upper surface of the rotating substrate W. The aqueous phosphoric acid solution on the substrate W is washed by the pure water discharged from the eluent nozzle 22. Thereby, a liquid film of pure water covering the upper surface of the substrate W is formed. When the eluent valve 24 is turned on and the predetermined time elapses, the eluent valve 24 is closed to stop the discharge of pure water.

In the first eluent supply step, the treatment liquid (mainly eluent) guided to the cup 12 by the baffle 11 is discharged through the drain pipe 81.

Next, an SC1 supply step of supplying SC1 to the substrate W is performed (step S5). Specifically, the second nozzle moving unit 21 moves the SC1 nozzle 18 to the processing position, and the shutter raising and lowering unit 13 faces the substrate W different from the substrate W in the phosphoric acid supply step. Thereafter, the SC1 valve 20 is opened, and the SC1 nozzle 18 starts to discharge SC1. When SC1 is discharged from SC1 nozzle 18, second nozzle moving unit 21 may be a central processing position for causing SC1 nozzle 18 to be liquided from SC1 discharged from SC1 nozzle 18 to the center of the upper surface of substrate W, and from SC1 nozzle. The SC1 discharged is moved to the outer peripheral processing position of the outer peripheral portion of the upper surface of the substrate W. Further, the SC1 may be stationary such that the position of the SC1 is located at the central portion of the upper surface of the substrate W.

The SC1 discharged from the SC1 nozzle 18 is applied to the upper surface of the substrate W, and then flows along the upper surface of the rotating substrate W. Thereby, a liquid film of SC1 covering the entire upper surface of the substrate W is formed, and SC1 is supplied to the entire upper surface of the substrate W. When the SC1 valve 20 is turned on and the predetermined time elapses, the SC1 valve 20 is closed to stop the discharge of SC1 from the SC1 nozzle 18. Thereafter, the second nozzle moving unit 21 moves the SC1 nozzle 18 to the retracted position.

The SC1 supplied to the upper surface of the substrate W is caused to fly toward the outside of the substrate W by centrifugal force, and is guided by the baffle 11 facing the substrate W, and guided to the corresponding cup 12. Similarly to the phosphoric acid aqueous solution, the SC1 system can be recovered in the SC1 tank (not shown) and reused, or discarded without being recovered.

Next, a second eluent supply step of supplying pure water, which is one example of the eluent, to the upper surface of the substrate W is performed (step S6). Specifically, the eluent valve 24 is opened, and pure water is discharged from the eluent nozzle 22. The pure water that has been liquided to the upper surface of the substrate W flows outward along the upper surface of the rotating substrate W. Thereby, the SC1 on the substrate W is washed by pure water to form a liquid film of pure water covering the entire upper surface of the substrate W. When the eluent valve 24 is turned on and the predetermined time elapses, the eluent valve 24 is closed to stop the discharge of pure water.

In the second eluent supply step, the treatment liquid (mainly eluent) guided to the cup 12 by the baffle 11 is discarded.

Next, a drying step of drying the substrate W is performed by high-speed rotation of the substrate W (step S7). Specifically, the rotation motor 9 accelerates the rotation of the substrate W to rotate the substrate W at a larger rotation speed (for example, thousands of rpm) than in the liquid processing steps (S3 to S6). Thereby, the liquid system on the substrate W is removed by centrifugal force, and the substrate W is dried. When the high-speed rotation of the substrate W is started and the predetermined time elapses, the rotation is performed. The rotation of the rotary motor 9 is stopped (step S8).

Thereafter, a carry-out step of carrying out the substrate W from the chamber 4 is performed (step S9). Specifically, the shutter lifting unit 13 lowers all of the shutters 11 to the lower position. Thereafter, the transfer robot causes the robot to enter the chamber 4, and takes the processed substrate W from the spin chuck 5 and carries it out of the chamber 4.

Fig. 6 is a flow chart for explaining a process associated with the supply of an aqueous phosphoric acid solution. The control device 3 turns on the phosphoric acid valve 16 and supplies the phosphoric acid aqueous solution to the phosphoric acid nozzle 14 (step S11). Thereby, the phosphoric acid aqueous solution is supplied to the substrate W held by the rotary chuck 5. On the other hand, the control device 3 opens the recovery valve 72 and closes the liquid discharge valve 82. Thereby, the used phosphoric acid aqueous solution supplied to the substrate W is recovered into the supply tank 31 via the recovery pipe 71 (step S12).

On the other hand, the control device 3 determines whether or not the condition (supplement start condition) at which the supply of the new liquid to the supply tank 31 is to be started is satisfied (step S13). Specifically, the supplemental start condition may also include a liquid amount condition. One of the liquid amount conditions is a specific example in which the lower limit sensor 44L detects the liquid amount below the lower limit value. In addition, the supplemental start condition may also include a processing number condition. One of the processing conditions is a specific example in which the number of substrates W to be processed reaches a predetermined number of sheets without replenishing the new liquid to the supply tank 31. Further, the supplemental start condition may also include a sputum concentration condition. Specifically, one of the enthalpy concentration conditions is that the cerium concentration in the aqueous phosphoric acid solution supplied from the supply tank 31 toward the phosphoric acid nozzle 14 reaches a predetermined concentration. Alternatively, when at least one of the liquid amount condition, the treatment number condition, and the helium concentration condition is satisfied, the control device 3 determines that the supplementary start condition is satisfied. The control device 3 may, for example, open the valves 38 and 39 at predetermined time intervals (for example, at intervals of 10 minutes to several tenths), sample the phosphoric acid aqueous solution, and introduce it into the helium concentration meter 37 to measure the enthalpy concentration.

When the replenishment start condition is satisfied, in order to replenish the new liquid to the supply tank 31 from the fresh liquid replenishing system 50, the control device 3 determines the amount of liquid to be replenished (step S14). The total amount of liquid to be replenished may be, for example, a difference between the lower limit value detected by the lower limit sensor 44L and the target value detected by the target sensor 44t, which is a known value. When the supplementary start condition is satisfied by the satisfaction of the processing number condition or the enthalpy concentration condition, there is a possibility that the liquid amount in the supply tank 31 is more than the lower limit value. In such a case, the control device 3 may open the discharge valve 42 to drain the phosphoric acid aqueous solution in the supply tank 31 until the liquid amount in the supply tank 31 becomes the lower limit value.

The control device 3 determines the amount of replenishing liquid by mixing the phosphoric acid aqueous solution in the supply tank 31, the new liquid prepared in the new liquid mixing tank 51 (the unused antimonic acid aqueous solution having the reference enthalpy concentration), and the phosphate raw liquid. On the other hand, the phosphoric acid aqueous solution having the reference enthalpy concentration (adjustment target value) is stored in the supply tank 31 until the liquid level of the target value. The sum of the replenishing amount of the new liquid and the replenishing amount of the phosphoric acid stock solution is the total amount of the replenished liquid, as described above, and the value is known. Further, since the amount of liquid in the supply tank 31 is replenished in the state of the lower limit value, the amount of the phosphoric acid aqueous solution in the supply tank 31 at the start of replenishment is also known. Therefore, when the concentration of ruthenium in the aqueous phosphoric acid solution in the supply tank 31 at the start of the replenishment is known, the control device 3 can determine the amount of replenishment of the new liquid and the amount of replenishment of the phosphate stock solution. In other words, the ratio of the amount of fresh liquid replenished to the amount of phosphate stock replenished can be determined.

The ruthenium concentration in the phosphoric acid aqueous solution recovered in the supply tank 31 by the recovery pipe 71 is higher than the ruthenium concentration in the phosphoric acid aqueous solution supplied from the phosphoric acid valve 16 to the substrate W. This is because the ruthenium material (containing the ruthenium compound) constituting the substrate W is eluted into the phosphoric acid aqueous solution. The elution amount differs depending on the type of the substrate W, and is different depending on the conditions for the treatment of the substrate W. The control device 3 can obtain the self from the recipe R Wait for information.

Further, since the phosphoric acid aqueous solution is repeatedly collected in the supply tank 31 by the recovery pipe 71, the concentration of ruthenium in the phosphoric acid aqueous solution in the supply tank 31 increases as the number of substrates processed increases. That is, the concentration of ruthenium in the aqueous phosphoric acid solution depends on the number of treatments. The control device 3 can obtain information related to the number of processes by counting the number of processed substrates.

On the other hand, the ruthenium concentration of the aqueous phosphoric acid solution in the supply tank 31 also depends on the recovery rate of the phosphoric acid aqueous solution. The recovery ratio refers to the ratio of the amount of the phosphoric acid aqueous solution recovered in the supply tank 31 through the recovery pipe 71 to the amount of the phosphoric acid aqueous solution discharged from the phosphoric acid nozzle 14 . In the rinsing step, since one part of the aqueous phosphoric acid solution is discharged together with the eluent (pure water), the recovery rate is less than 100%. The control device 3 can obtain information related to the recovery rate by referring to the recipe R. Of course, the operator can also operate the input device 96 to input information related to the recovery rate.

Thus, the control device 3 is obtained from the information obtained by the formulation R (the amount of elution of the crucible (the type of the substrate W and/or the condition of the substrate processing), the recovery rate), and the process obtained in the process of controlling the substrate processing apparatus 1. Information (number of processes), information input by the input device 96, and the like are used to determine the concentration of germanium in the aqueous phosphoric acid solution at the beginning.

Further, the concentration of ruthenium in the phosphoric acid aqueous solution recovered in the supply tank 31 can be determined by calculation, and the corresponding 矽 can be used with respect to the type of the substrate W, the conditions of the substrate processing, the recovery rate, the number of processes, and the like. Find the table of concentration values. Further, a table corresponding to the new liquid replenishing amount and the phosphoric acid stock replenishing amount may be prepared with respect to the type of the substrate W, the conditions of the substrate processing, the recovery rate, the number of processes, and the like.

Thereby, the control device 3 determines the amount of new liquid replenishment and the phosphate solution supplement Amount (step S14). Further, the control device 3 opens the new liquid replenishing valve 53, drives the pump 54, and replenishes the new liquid from the new liquid mixing tank 51 toward the supply tank 31 (step S15). This replenishment amount is measured using the integrated flow meter 61. When the measured value of the integrated flow meter 61 reaches the new liquid replenishing amount (step S16), the control device 3 stops the pump 54 and closes the new liquid replenishing valve 53 (step S17). Further, the control device 3 opens the phosphate raw material replenishing valve 60, and the phosphate raw material solution is replenished to the supply tank 31 via the phosphoric acid stock solution replenishing pipe 59 (step S18). This replenishment amount is measured using the integrated flow meter 62. When the measured value of the integrated flow meter 62 reaches the phosphoric acid stock replenishing amount (step S19), the control device 3 closes the phosphoric acid stock replenishing valve 60 to stop the replenishment of the phosphoric acid stock solution (step S20).

As described above, according to the present embodiment, the substrate W is processed by using an aqueous phosphoric acid solution, and the tantalum nitride film Fn exposed on the surface of the substrate W is selectively etched. The concentration of ruthenium contained in the aqueous phosphoric acid solution is controlled to a predetermined ruthenium concentration range, whereby etching of the ruthenium oxide film Fo exposed on the surface of the substrate W can be suppressed, whereby the tantalum nitride film Fn can be improved. The choice ratio.

The phosphoric acid aqueous solution is supplied from the supply tank 31 to the phosphoric acid nozzle 14 and is supplied from the phosphoric acid nozzle 14 to the substrate W. The used phosphoric acid aqueous solution used in the processing of the substrate W is recovered in the supply tank 31. When the predetermined supplemental start condition is satisfied (step S13: satisfied), the new stock containing the ruthenium at the reference ruthenium concentration and the phosphate stock solution having the ruthenium concentration of zero are replenished to the supply tank 31. By appropriately determining the respective replenishing amounts of the new liquid and the phosphoric acid stock solution, the rhodium concentration of the phosphoric acid aqueous solution in the supply tank 31 can be controlled to a predetermined crucible concentration range.

The new liquid and the phosphoric acid raw liquid of the reference enthalpy concentration are prepared in advance, and are supplied to the supply tank 31 only in a required amount as needed, whereby the cerium concentration of the phosphoric acid aqueous solution in the supply tank 31 can be adjusted to a predetermined cerium concentration range (preferably As the reference concentration). Thus, no Since the waiting time for replenishing the phosphoric acid aqueous solution to the supply tank 31 is required, the productivity of the substrate treatment is not impaired, and a stable aqueous solution of phosphoric acid having a helium concentration can be supplied to the substrate W.

Further, since it is only necessary to prepare a new liquid having a reference enthalpy concentration and a phosphate stock solution in advance, it is not necessary to immediately control the erbium concentration of the phosphoric acid aqueous solution. As described above, the concentration of the phosphoric acid aqueous solution and the new liquid stored in the supply tank 31 can be confirmed by the krypton concentration meter 37. However, the cerium concentration meter 37 is not an essential configuration, and it is not necessary to immediately monitor the composition of the cerium concentration in the aqueous phosphoric acid solution. Therefore, it is possible to supply a stable aqueous solution of phosphoric acid having a stable concentration to the substrate W at a low cost.

Further, in the present embodiment, the new liquid system supplied from the new liquid mixing tank 51 to the supply tank 31 has a helium concentration (more specifically, a reference helium concentration) within a predetermined concentration range. Therefore, the cerium concentration of the phosphoric acid aqueous solution in the supply tank 31 is easily guided to a value within a predetermined erbium concentration range by the supply of the new liquid. Further, when the phosphoric acid aqueous solution is first stored in the supply tank 31, only the new liquid to be blended in the new liquid mixing tank 51 may be supplied to the supply tank 31. Thereby, the phosphoric acid aqueous solution stored in the supply tank 31 can be quickly used in the processing of the substrate W without going through the standby time for achieving uniformization of the concentration.

Further, since the phosphate raw material having a niobium concentration of zero can be replenished to the supply tank 31 via the phosphate stock solution replenishing pipe 59, the niobium concentration of the phosphoric acid aqueous solution in the supply tank 31 can be easily guided to a value within a predetermined niobium concentration range. In particular, when the substrate W contains ruthenium, the phosphoric acid aqueous solution is supplied to the substrate W, and the ruthenium of the substrate material is eluted into the phosphoric acid aqueous solution. Therefore, the concentration of the phosphoric acid aqueous solution recovered in the supply tank 31 becomes higher. It is higher before the substrate W. Here, the phosphate stock solution containing ruthenium is contained by a concentration lower than the predetermined ruthenium concentration range (zero in the present embodiment). The supply to the supply tank 31 can easily guide the ruthenium concentration of the phosphoric acid aqueous solution in the supply tank 31 to a predetermined ruthenium concentration range.

Further, in the present embodiment, the amount of replenishment of the new liquid and the phosphoric acid stock solution into the supply tank 31 is determined based on the type of the substrate W. The fluctuation of the ruthenium concentration in the aqueous phosphoric acid solution after the substrate treatment can be predicted based on the type of the substrate W. Here, the respective amounts of the fresh liquid and the phosphoric acid stock solution can be determined based on the type of the substrate W, whereby the germanium concentration of the phosphoric acid aqueous solution in the supply tank 31 can be appropriately adjusted.

The amount of ruthenium eluted from the substrate W by the treatment with the phosphoric acid aqueous solution differs depending on the type of the substrate W or the like. The amount of cesium dissolved greatly affects the concentration of ruthenium in the recovered aqueous phosphoric acid solution. Here, the amount of the ruthenium eluted from the substrate W is specified depending on the type of the substrate W, etc., and the respective amounts of the new liquid and the phosphoric acid stock solution are determined based on the specific amount of enthalpy eluted, thereby appropriately The ruthenium concentration of the aqueous phosphoric acid solution in the supply tank 31 is adjusted.

Further, in the present embodiment, the supply amount of the fresh liquid and the phosphoric acid stock solution is determined based on the recovery rate of the phosphoric acid aqueous solution recovered in the supply tank 31 from the phosphoric acid aqueous solution supplied from the phosphoric acid nozzle 14 to the substrate W. Thereby, the erbium concentration of the phosphoric acid aqueous solution in the supply tank 31 can be adjusted to a predetermined erbium concentration range while the required amount of the phosphoric acid aqueous solution is replenished to the supply tank 31.

Further, in the present embodiment, the respective amounts of the fresh liquid and the phosphoric acid stock solution are determined based on the number of sheets (the number of processes) of the substrate W to be processed by the phosphoric acid aqueous solution supplied from the phosphoric acid nozzle 14. Thereby, the ruthenium concentration of the phosphoric acid aqueous solution in the supply tank 31 can be appropriately adjusted.

Further, in the present embodiment, the above-described supplementary start condition includes a liquid amount condition relating to the amount of liquid stored in the supply tank 31. Specifically, it will be stored in When the amount of liquid in the supply tank 31 is reduced to the lower limit value, the new liquid and the phosphate raw liquid are replenished as a trigger condition. Thereby, when the amount of liquid in the supply tank 31 is reduced to the lower limit value, the new liquid and the phosphoric acid raw liquid are replenished to restore the liquid amount, and the enthalpy concentration is adjusted.

Further, in the present embodiment, the supplementary start condition includes a number of processing conditions relating to the number of substrates W to be processed by the phosphoric acid aqueous solution supplied from the phosphoric acid nozzle 14. That is, when the number of sheets of the substrate W to be processed reaches a predetermined number, it is used as a trigger condition, and the new liquid and the phosphoric acid stock solution are replenished to the supply tank 31. Thereby, the substrate W can be treated with a stable aqueous solution of phosphoric acid.

Further, in the present embodiment, the supplementary start condition includes a enthalpy concentration condition relating to the erbium concentration in the phosphoric acid aqueous solution supplied from the supply tank 31 toward the phosphoric acid nozzle 14. Specifically, the concentration of ruthenium in the aqueous phosphoric acid solution which is cyclically tempered by the circulation pipe 32 is periodically measured by the helium concentration meter 37. When the measured value rises to a predetermined value, it is used as a trigger condition, and the new liquid and the phosphoric acid stock solution are replenished to the supply tank 31. Thereby, since the ruthenium concentration of the phosphoric acid aqueous solution in the supply tank 31 is returned to the predetermined erbium concentration range, the substrate W can be treated with a stable cesium concentration phosphoric acid aqueous solution.

Further, in the present embodiment, the substrates W are horizontally held by the rotary chuck 5 one by one and processed. In such a so-called monolithic process, it is important to accurately adjust the concentration of ruthenium in the aqueous phosphoric acid solution discharged from the phosphoric acid nozzle 14. When the adjustment of the erbium concentration is insufficient, there is a problem that the processing quality is uneven between the plurality of substrates W to be processed. In the process of the present embodiment, the concentration of germanium in the phosphoric acid aqueous solution supplied from the supply tank 31 to the phosphoric acid nozzle 14 is accurately and stably controlled. Therefore, substrate processing with less processing quality can be achieved.

Further, in the present embodiment, the measurement is performed by the integrated flow meter 61. The new liquid replenishing amount of the supply tank 31 is measured by the integrated flow meter 62 to measure the amount of the phosphate raw liquid replenishment to the supply tank 31. The control device 3 manages the new liquid replenishing amount and the phosphoric acid stock replenishing amount based on the measurement results of the integrated flow meters 61 and 62. Thereby, the concentration of ruthenium in the aqueous phosphoric acid solution in the supply tank 31 can be accurately adjusted.

FIG. 7 is a schematic view showing the configuration of the substrate processing apparatus 1 according to the second embodiment of the present invention, and mainly shows the configuration of the phosphoric acid supply system 30. In FIG. 7, parts corresponding to those in FIG. 2 are denoted by the same reference symbols.

The phosphoric acid supply system 30 of the substrate processing apparatus 1 includes a first recovery tank 90A and a second recovery tank 90B. The recovery pipe 71 is divided into two recovery branch pipes 71A and 71B. The first recovery branch pipe 71A is connected to the first recovery tank 90A, and the second recovery branch pipe 71B is connected to the second recovery tank 90B. The first recovery valve 72A and the second recovery valve 72B are interposed between the first recovery branch pipe 71A and the second recovery branch pipe 71B. By opening the first recovery valve 72A and closing the second recovery valve 72B, the used phosphoric acid aqueous solution used for substrate processing is recovered in the first recovery tank 90A. By closing the first recovery valve 72A and opening the second recovery valve 72B, the used phosphoric acid aqueous solution is recovered to the second recovery tank 90B. The control device 3 controls the opening and closing of the first and second recovery valves 72A and 72B, and selects the recovery destination of the used phosphoric acid aqueous solution as one of the first recovery tank 90A and the second recovery tank 90B (recycling purpose) Ground selection step).

On the other hand, the phosphoric acid aqueous solution stored in the first recovery tank 90A and the second recovery tank 90B is replenished to the supply tank 31 via the supplementary piping 100 (mixing liquid supply piping). The downstream end of the supplementary pipe 100 is connected to the supply tank 31. The upstream end of the supplementary pipe 100 is divided into a first branch pipe 100A and a second branch pipe 100B. The first branch pipe 100A is connected to the first recovery tank 90A, and the second branch pipe 100B is connected to the second recovery tank 90B. The first supplemental valve 101A and the second section are interposed between the first branch pipe 100A and the second branch pipe 100B. The valve 101B is replenished. A pump 102 and a heater 103 are interposed in the supplementary pipe 100.

When the pump 102 is driven in a state where the first replenishing valve 101A is opened and the second replenishing valve 101B is closed, the phosphoric acid aqueous solution can be supplied from the first recovery tank 90A to the supply tank 31. When the pump 102 is driven in a state where the first replenishing valve 101A is closed and the second replenishing valve 101B is opened, the phosphoric acid aqueous solution can be supplied from the second recovery tank 90B to the supply tank 31. When the pipe 100 is replenished, the phosphoric acid aqueous solution is heated by the heater 103. Therefore, the temperature-adjusted aqueous phosphoric acid solution can be supplied to the supply tank 31.

The control device 3 selects one of the first recovery tank 90A and the second recovery tank 90B by controlling the opening and closing of the first and second supplementary valves 101A and 101B to supplement the source of the phosphoric acid aqueous solution to the supply tank 31. More specifically, the control device 3 selects the recovery tanks 90A and 90B that are not selected as the recovery destinations of the used phosphoric acid aqueous solution as a supplementary source to the supply tank 31 (supplement source selection step).

The new liquid supply pipe 52 through which the new liquid supplied from the fresh liquid mixing tank 51 flows is divided into the first branch pipe 52A and the second branch pipe 52B. The first branch pipe 52A is connected to the first recovery tank 90A, and the second branch pipe 52B is connected to the second recovery tank 90B. The first new liquid replenishing valve 53A and the second new liquid replenishing valve 53B are respectively disposed in the first branch pipe 52A and the second branch pipe 52B.

By opening the first fresh liquid replenishing valve 53A, the new liquid (the unused phosphoric acid aqueous solution having the reference enthalpy concentration) to be blended in the new liquid mixing tank 51 can be supplied to the first recovery tank 90A. Similarly, by opening the second fresh liquid replenishing valve 53B, the new liquid to be blended in the new liquid mixing tank 51 can be supplied to the second recovery tank 90B.

The phosphate stock replenishing pipe 59 is divided into a first branch pipe 59A and a second branch pipe 59B. The first branch pipe 59A is connected to the first recovery tank 90A, and the second branch pipe 59B is connected to the second recovery tank 90B. The first branch pipe 59A and the second branch pipe 59B are respectively introduced. The first phosphate raw material replenishing valve 60A and the second phosphoric acid raw material replenishing valve 60B are provided. By opening the first phosphate stock solution replenishing valve 60A, the phosphate stock solution (aqueous phosphoric acid solution not containing ruthenium) can be supplied to the first recovery tank 90A. Similarly, the phosphoric acid stock solution can be supplied to the second recovery tank 90B by opening the second phosphoric acid stock solution replenishing valve 60B.

The control device 3 controls the opening and closing of the first and second fresh liquid replenishing valves 53A and 53B and the first and second phosphoric acid replenishing valves 60A and 60B, and selects the replenishment destination of the new liquid and the phosphoric acid raw liquid as the first. Any one of the recovery tank 90A and the second recovery tank 90B. More specifically, the control device 3 selects the recovery tanks 90A and 90B selected as the collection destinations of the used phosphoric acid aqueous solution as the replenishment destinations of the new liquid and the phosphoric acid raw liquid (supply destination selection step).

In order to discharge the phosphoric acid aqueous solution in the first and second recovery tanks 90A and 90B, respectively, first and second discharge systems 45A and 45B are provided. The discharge systems 45A and 45B include discharge pipes 46A and 46B which discharge the phosphoric acid aqueous solution in the recovery tanks 90A and 90B, and discharge valves 47A and 47B which are disposed in the discharge pipes 46A and 46B. A discharge flow rate adjustment valve for adjusting the discharge flow rate of the phosphoric acid aqueous solution may be disposed in the discharge pipes 46A and 46B.

When the discharge valves 47A and 47B are opened, the phosphoric acid aqueous solution in the recovery tanks 90A and 90B is discharged to the discharge pipes 46A and 46B. Thereby, the amount of the phosphoric acid aqueous solution in the recovery tanks 90A and 90B can be reduced as needed, or all of the phosphoric acid aqueous solutions in the recovery tanks 90A and 90B can be drained.

In order to detect the amount of liquid stored in the first and second recovery tanks 90A and 90B, the lower limit liquid amount sensors 75A and 75B, the recovery stop liquid amount sensors 76A and 76B, and the target liquid amount sensors 77A and 77B are provided. When the phosphoric acid aqueous solution is supplied from the recovery tanks 90A and 90B to the supply tank 31 to reduce the amount of liquid in the recovery tanks 90A and 90B, The lower limit liquid amount sensors 75A, 75B detect the reaching of the lower limit liquid amount. When the used phosphoric acid aqueous solution is recovered in the recovery tanks 90A and 90B and the amount of liquid in the recovery tanks 90A and 90B is increased, the recovery stop amount sensors 76A and 76B detect the amount of liquid to be recovered to the upper limit. When the unused aqueous phosphoric acid solution is replenished to the recovery tanks 90A, 90B in the fresh liquid replenishing system 50 to increase the amount of liquid in the recovery tanks 90A, 90B, the target liquid amount sensors 77A, 77B are detected until they are to be stopped. Liquid volume (target liquid volume).

Further, in the present embodiment, the valve 29 is interposed in the circulation pipe 32. In the configuration shown in Fig. 2, a valve 29 as such can also be provided. The valve 29 is opened and closed by the control device 3.

Fig. 8 is a block diagram for explaining an electrical configuration of the substrate processing apparatus 1 of the configuration of Fig. 7. In FIG. 8, portions corresponding to those of FIG. 3 described above are denoted by the same reference symbols. The control device 3 controls the processing unit 2 and the phosphoric acid supply system 30. Regarding the phosphoric acid supply system 30, the control device 3 controls the pumps 33, 54, 102, controls the heaters 34, 103, and controls the valves 38, 39, 42, 53A, 53B, 56, 58, 60A, 60B, 64, 65, 72A, 72B. Further, an output signal of the liquid amount sensor 44 of the supply tank 31, an output signal of the concentration meter 37, an output signal of the integrated flow meters 61, 62, and a liquid amount sensor of the recovery tanks 90A, 90B are input to the control device 3. Output signals of 75A, 75B, 76A, 76B, 77A, 77B.

9, 10 and 11 are flowcharts for explaining processing associated with supply of an aqueous phosphoric acid solution. Fig. 9 shows an operation related to the supply of the phosphoric acid aqueous solution to the substrate W and the addition of the phosphoric acid aqueous solution to the supply tank 31. Fig. 10 shows the selection of the recovery destination of the used phosphoric acid and the selection of the source of the phosphoric acid aqueous solution to the supply tank 31. The operation of Fig. 11 shows the operation related to the replenishment of the new liquid to the recovery tanks 90A, 90B.

First, referring to Fig. 9, the control device 3 turns on the phosphoric acid valve 16 to supply the phosphoric acid aqueous solution to the phosphoric acid nozzle 14 (step S21). Thereby, the phosphoric acid aqueous solution is supplied to the substrate W held by the rotary chuck 5. The amount of the phosphoric acid aqueous solution supplied to the tank 31 by the supply of the phosphoric acid aqueous solution is reduced. Next, when the liquid amount of the phosphoric acid aqueous solution in the supply tank 31 is detected by the lower limit sensor 44L to be the lower limit value (step S22: YES), the control device 3 is selected from any one selected as a supplementary source of the phosphoric acid aqueous solution. The grooves 90A and 90B are supplied with a phosphoric acid aqueous solution to the supply tank 31 (step S23). That is, the control device 3 turns on the replenishing valves 101A, 101B corresponding to any of the recovery tanks 90A, 90B selected as the supplementary source, and drives the pump 102. When the target sensor 44t detects that the amount of the phosphoric acid aqueous solution in the supply tank 31 has reached the target value due to the replenishing operation (step S24: YES), the control device 3 ends the replenishing operation (step S25). By repeating the same operation, the amount of the phosphoric acid aqueous solution in the supply tank 31 is maintained in an appropriate range between the lower limit value and the target value.

Next, referring to Fig. 10, the control device 3 selects the recovery destination of the used phosphoric acid aqueous solution used for the substrate processing as one of the recovery tanks 90A and 90B (step S31), and among them The other is selected as a supplemental source of the phosphoric acid aqueous solution toward the supply tank 31 (step S32).

In other words, the recovery valves 72A and 72B corresponding to the recovery tanks 90A and 90B selected as the recovery destinations are opened, and the recovery valves 72A and 72B corresponding to the recovery tanks 90A and 90B which are not selected as the recovery destinations are closed. . Further, when it is necessary to supply the phosphoric acid aqueous solution to the supply tank 31 (step S22 in Fig. 9), the replenishing valves 101A and 101B corresponding to the recovery tanks 90A and 90B selected as the source of the phosphoric acid aqueous solution are opened, and are supplemented as a phosphoric acid aqueous solution. The replenishing valves 101A and 101B corresponding to the uncollected recovery tanks 90A and 90B are kept in a closed state.

Further, when the lower limit liquid amount sensors 75A and 75B corresponding to the recovery tanks 90A and 90B selected as the supplementary sources detect that the liquid amounts of the recovery tanks 90A and 90B are reduced to the lower limit liquid amount (step S33: YES), The control device 3 switches the recovery destination and the phosphoric acid aqueous solution supplement source (steps S31 and S32). In other words, the recovery tanks 90A and 90B until the liquid amount is reduced to the lower limit liquid amount are selected as the recovery destinations (step S31), and the other recovery tanks 90A and 90B are selected as the phosphoric acid aqueous solution supplement source (step S32).

By repeating the same operation, the first recovery tank 90A and the second recovery tank 90B use a lower liquid amount as a trigger point, and the task is to alternately switch between the recovery destination and the phosphoric acid aqueous solution supplement source.

Next, referring to Fig. 11, the control device 3 determines whether or not the new liquid is to be replenished to the recovery tanks 90A and 90B selected as the collection destination (step S41). Specifically, the control device 3 determines whether or not the condition (supplement start condition) at which the new liquid should be replenished to the recovery tanks 90A and 90B is satisfied. The replenishment start condition may also include a liquid amount condition (recovery liquid amount condition). In one specific example of the liquid amount condition, the amount of the recovered liquid stored in the recovery tanks 90A and 90B selected as the recovery destination is increased, and the recovery stop liquid amount sensors 76A and 76B corresponding to the recovery stop liquid amount are detected. In addition, the supplemental start condition may also include a processing number condition. A specific example of the number of processing conditions is that the number of substrates W to be processed reaches a predetermined number of sheets without replenishing the new liquid to the recovery tanks 90A and 90B. Further, the supplemental start condition may also include a sputum concentration condition. In one specific example of the cerium concentration condition, the cerium concentration in the phosphoric acid aqueous solution supplied from the supply tank 31 toward the phosphoric acid nozzle 14 reaches a predetermined concentration. Alternatively, when at least one of the liquid amount condition, the treatment number condition, and the helium concentration condition is satisfied, the control device 3 determines that the supplementary start condition is satisfied.

When the supplemental start condition is satisfied (step S41: satisfied), the control device 3 stops the recovery operation (step S42). In other words, the control device 3 closes the recovery valves 72A and 72B corresponding to the recovery tanks 90A and 90B selected as the recovery destination, and opens the liquid discharge valve 82.

Further, in order to replenish the new liquid to the recovery tanks 90A and 90B of the recovery destination from the fresh liquid replenishing system 50, the control device 3 determines the amount of liquid to be replenished (step S43). The total amount of the liquid to be replenished may be, for example, the amount of the recovery stop liquid detected by the recovery stop amount sensors 76A, 76B of the recovery tanks 90A, 90B of the recovery destination and the target liquid amount sensors 77A, 77B. The difference in the target liquid amount, which is a known value. When the replenishment start condition is satisfied because the processing number condition or the helium concentration condition is satisfied, there is a possibility that the liquid amount in the recovery tanks 90A and 90B at the recovery destination is larger than the recovery stop liquid amount. In such a case, the control device 3 may open the corresponding discharge valves 47A and 47B, and discharge the phosphoric acid aqueous solution in the recovery tanks 90A and 90B until the liquid amount in the recovery tanks 90A and 90B becomes The amount of stopped liquid is recovered.

The control device 3 determines the amount of replenishing liquid in which the phosphoric acid aqueous solution in the recovery tanks 90A and 90B selected as the recovery destination and the new liquid in the new liquid mixing tank 51 are mixed (the reference enthalpy concentration is not used). The phosphoric acid aqueous solution and the phosphoric acid stock solution are stored in the recovery tanks 90A and 90B to the target liquid amount by the reference cesium concentration (adjustment target value). The sum of the new liquid replenishing amount and the phosphoric acid stock replenishing amount is the total amount of the replenished liquid, which is known as described above. Further, since the amount of liquid in the recovery tanks 90A and 90B is replenished in a state where the amount of the stopped liquid is recovered, the amount of the phosphoric acid aqueous solution in the recovery tanks 90A and 90B at the start of the replenishment is also known. Therefore, if it is known that the phosphoric acid is dissolved in the recovery tanks 90A, 90B at the beginning of the replenishment The concentration of the ruthenium in the liquid, the control device 3 can determine the amount of the new liquid and the amount of the phosphate solution. In other words, the ratio of the amount of fresh liquid replenished to the amount of phosphate stock replenished can be determined.

The concentration of ruthenium in the aqueous phosphoric acid solution recovered in the recovery tanks 90A, 90B can be predicted based on the formulation or the number of sheets processed. This is related to the first embodiment and is as described above. As in the case of the first embodiment, the enthalpy concentration can be obtained by calculation, and a table corresponding to the enthalpy concentration value can be used with respect to the type of the substrate W, the conditions of the substrate processing, the recovery rate, the number of processes, and the like. To find out. Further, a table corresponding to the new liquid replenishing amount and the phosphoric acid stock replenishing amount may be prepared with respect to the type of the substrate W, the conditions of the substrate processing, the recovery rate, the number of processes, and the like.

In this manner, the control device 3 determines the amount of new liquid replenishment and the amount of replenishment of the phosphoric acid solution (step S43). Next, the control device 3 opens the replenishing valves 53A and 53B corresponding to the recovery tanks 90A and 90B selected as the recovery destinations, drives the pump 54, and replenishes the new liquid from the new liquid mixing tank 51 toward the recovery tanks 90A and 90B ( Step S44). This replenishment amount is measured by the integrated flow meter 61. When the measured value of the integrated flow meter 61 reaches the new liquid replenishing amount (step S45: YES), the control device 3 stops the pump 54, and closes the replenishing valves 53A, 53B (step S46). In addition, the control device 3 opens the phosphate raw material replenishing valves 60A and 60B corresponding to the recovery tanks 90A and 90B selected as the recovery destinations, and supplies the phosphate raw liquid to the recovery tanks 90A and 90B via the phosphoric acid raw material piping 55 (step S47). ). This replenishment amount is measured using the integrated flow meter 62. When the measured value of the integrated flow meter 62 reaches the phosphoric acid stock replenishing amount (step S48: YES), the control device 3 closes the first phosphoric acid stock replenishing valve 60A to stop the replenishment of the phosphoric acid stock solution (step S49).

By repeating such an operation, the recovery tanks 90A and 90B which are selected as the recovery destinations are not the recovery tanks 90A and 90B which are not supplied to the phosphoric acid aqueous solution of the supply tank 31, and the phosphoric acid aqueous solution having the reference enthalpy concentration can be previously adjusted. Thanks back Since the collection destination and the phosphoric acid aqueous solution supplement source are alternately switched as described above, the phosphoric acid aqueous solution blending operation by the new liquid replenishment of the first and second recovery tanks 90A and 90B is interactively performed.

As described above, in the present embodiment, the tank for storing the phosphoric acid aqueous solution includes the first and second recovery tanks 90A and 90B, and the phosphoric acid used for the substrate treatment is introduced through the recovery pipe 71. The aqueous solution; and the supply tank 31 are supplied with the phosphoric acid aqueous solution stored in the first and second recovery tanks 90A and 90B via the supplementary piping 100. Next, the phosphoric acid aqueous solution stored in the supply tank 31 is supplied to the phosphoric acid nozzle 14 via the phosphate pipe 15. The new liquid replenishing system 50 supplies an unused aqueous phosphoric acid solution (new liquid and phosphoric acid stock solution) to the recovery tanks 90A and 90B.

The adjustment of the ruthenium concentration in the phosphoric acid aqueous solution is carried out in the recovery tanks 90A and 90B, and the phosphoric acid aqueous solution whose enthalpy concentration has been adjusted is transported from the recovery tanks 90A and 90B to the supply tank 31 via the supplementary piping 100. Therefore, the concentration of ruthenium in the aqueous phosphoric acid solution in the supply tank 31 is not affected by the liquid recovery and is stabilized. Thereby, a more stable aqueous solution of phosphoric acid having a stable concentration can be supplied from the phosphoric acid nozzle 14 to the substrate W.

Further, in the present embodiment, one of the first recovery tank 90A and the second recovery tank 90B is selected as a supplemental source of the phosphoric acid aqueous solution to the supply tank 31, and the other one is selected as the used phosphoric acid aqueous solution. Recycling destination. Thereby, the phosphoric acid aqueous solution whose enthalpy concentration has been adjusted can be supplied to the supply tank 31 without stagnation, so that the supply of the phosphoric acid aqueous solution to the substrate W does not stagnate. Thereby, the productivity of the substrate processing can be improved. Further, in the recovery tanks 90A and 90B for recovering the phosphoric acid aqueous solution, the new liquid and the phosphoric acid raw liquid are supplied to the recovered phosphoric acid aqueous solution to adjust the enthalpy concentration. Therefore, the concentration of ruthenium in the aqueous phosphoric acid solution in the recovery tanks 90A and 90B supplied to the supply tank 31 is stabilized, so that the phosphorus in the supply tank 31 can be stably maintained. The concentration of ruthenium in an aqueous acid solution. Thereby, the concentration of ruthenium used in the aqueous solution of phosphoric acid treated in the substrate is more stable.

FIG. 12 is a schematic view for explaining the configuration of the substrate processing apparatus 1 according to the third embodiment of the present invention. In FIG. 2, parts corresponding to those in FIG. 7 are denoted by the same reference symbols. In the embodiment, the new liquid replenishing system 50 includes the first fresh liquid mixing tank 51 and the second new liquid mixing tank 111. In the first fresh liquid mixing tank 51, a phosphate raw liquid is supplied from the phosphoric acid raw material piping 55 via the first phosphoric acid raw liquid valve 56, and the second fresh liquid mixing tank 111 is supplied from the second phosphoric acid raw liquid through the second phosphoric acid raw liquid valve 112. The piping 113 is supplied with a phosphate stock solution. In addition, the first fresh liquid mixing tank 51 is supplied with the hydrazine concentrate from the hydrazine concentrate pipe 57 via the first dam valve 58, and the second new liquid mixing tank 111 is passed through the second dam valve 114 from the second The hydrazine concentrate pipe 115 is supplied with a hydrazine concentrate.

The first fresh liquid mixing tank 51 is connected to the new liquid supply pipe 52 via the first fresh liquid supplement source selection valve 121. The second fresh liquid mixing tank 111 is connected to the new liquid supply pipe 52 via the second new liquid supply source selection valve 122. The second fresh liquid mixing tank 111, the second new liquid replenishing source selection valve 122, the pump 54, and the new liquid replenishing valves 53A and 53B constitute a third phosphoric acid aqueous solution supply means.

The control device 3 (see Fig. 8) controls the opening and closing of the above-described valves 112, 114, 121, and 122.

According to this configuration, the unused phosphoric acid aqueous solution to which the ruthenium is added can be supplied to the first recovery tank 90A and the second recovery tank 90B from the first fresh liquid mixing tank 51 and/or the second new liquid mixing tank 111.

The control device 3 is, for example, a phosphoric acid aqueous solution having a lower radon concentration (in the case of the first concentration) than the reference rhodium concentration in the first fresh liquid mixing tank 51. In addition, the control device 3 is a phosphoric acid aqueous solution in which the reference cerium concentration (the third concentration is exemplified) is blended in the second fresh liquid mixing tank 111.

When the substrate processing apparatus 1 is started to be used, the second new liquid replenishment source selection valve 122 is opened, and the first new liquid replenishment source selection valve 121 is closed, and the second new liquid mixing tank 111 is opposed to the recovery tanks 90A and 90B. One (for example, the first recovery tank 90A) is supplied with a phosphoric acid aqueous solution (new liquid) having a reference hydrazine concentration and stored. Next, the phosphoric acid aqueous solution having the reference enthalpy concentration is supplied from the first recovery tank 90A to the supply tank 31, and the phosphoric acid aqueous solution is used for substrate treatment.

On the other hand, in the other of the recovery tanks 90A and 90B (for example, the second recovery tank 90B), the used phosphoric acid aqueous solution is recovered. When the new liquid is mixed with the recovered phosphoric acid aqueous solution and adjusted to the reference enthalpy concentration, the control device 3 turns on the first new liquid replenishment source selection valve 121, and closes the second new liquid replenishment source selection valve 122. Thereby, the control device 3 supplies the new liquid having a lower enthalpy concentration than the reference enthalpy concentration to the second recovery tank 90B from the first fresh liquid mixing tank 51. Since the concentration of ruthenium in the used phosphoric acid aqueous solution is higher than the reference ruthenium concentration, the ruthenium concentration of the phosphoric acid aqueous solution in the second recovery tank 90B can be easily adjusted by mixing the phosphoric acid aqueous solution having a low ruthenium concentration.

Of course, in the stage where the number of substrates to be processed is small, the concentration of ruthenium in the aqueous phosphoric acid solution to be used repeatedly is not so high. Therefore, for example, it is also possible to add a new liquid having a reference enthalpy concentration from the second fresh liquid mixing tank 111 up to a predetermined number of processing sheets, and to add a low amount from the first new liquid mixing tank 51 when the number of predetermined processing sheets is exceeded. A new solution of bismuth concentration. Further, before the addition of the new liquid, the cerium concentration of the phosphoric acid aqueous solution in the recovery tanks 90A and 90B may be measured, and the first new liquid mixing tank 51 or the second new liquid mixing tank 111 may be selected in accordance with the measurement result. One is used as a supplement to the new fluid. Further, the first fresh liquid mixing tank 51 or the second new liquid may be blended in accordance with the type of the substrate W. Any of the slots 111 serves as a source of new fluid supplementation.

As described above, in the present embodiment, the first fresh liquid mixing tank 51 modulates a new liquid having a larger cerium concentration than that of the primary cerium concentration, and modulates the new liquid having the primary cerium concentration in the second fresh liquid mixing tank 111. Thereby, the enthalpy concentration adjustment range of the phosphoric acid aqueous solution in the recovery tanks 90A and 90B can be made large.

Although the embodiments of the present invention have been specifically described above, the present invention may be embodied in other forms. For example, in the above embodiment, a phosphoric acid aqueous solution having a reference ruthenium concentration, a zero-concentration phosphoric acid aqueous solution (phosphoric acid stock solution), and a phosphoric acid aqueous solution having a ruthenium concentration lower than the reference ruthenium concentration are exemplified as the used phosphoric acid aqueous solution to be recovered. An example of a mixed aqueous solution of phosphoric acid is used. However, it is also possible to use an aqueous solution of phosphoric acid having a concentration other than those of ruthenium.

Further, in the second and third embodiments, the configuration in which two collection grooves are provided is shown. However, it may be configured to have one recovery tank, or may have a configuration in which three or more recovery tanks are provided. However, by providing a plurality of (two or more) recovery tanks, it is possible to distinguish between a recovery tank that is a destination for recovery of the used phosphoric acid aqueous solution and a recovery tank that serves as a supplemental source to the supply tank, so that it is possible to The supply tank supplies a stable aqueous solution of phosphoric acid at a helium concentration.

Further, the configuration of the third embodiment including the first and second new liquid mixing tanks can be applied to the first embodiment shown in Fig. 2 .

The embodiments of the present invention have been described in detail, but these are only specific examples for illustrating the technical contents of the present invention, and the present invention should not be construed as limited to the specific examples. It is defined by the scope of the patent application.

Claims (26)

A substrate processing method for supplying a phosphoric acid aqueous solution containing germanium to a substrate having a hafnium oxide film and a tantalum nitride film exposed thereon, and selectively etching the tantalum nitride film; a step of storing the phosphoric acid aqueous solution in the cesium concentration range in the tank; supplying the phosphoric acid aqueous solution in the tank to the nozzle, supplying the phosphoric acid aqueous solution to the substrate from the nozzle to perform the substrate treatment; and supplying the nozzle from the nozzle to the substrate a step of recovering the aqueous solution of phosphoric acid used for the treatment of the substrate to the above-mentioned tank; a step of supplying the first aqueous solution of phosphoric acid having the first aqueous solution of phosphoric acid containing the ruthenium to the above-mentioned tank; The second concentration having a low concentration includes a second phosphoric acid aqueous solution supply step of supplying the second aqueous phosphoric acid solution having the ruthenium to the tank; and when the predetermined supplementary start condition is satisfied, the first phosphoric acid aqueous solution supply step and the second aqueous phosphoric acid solution are started. a determination step of the supply step; and determining the first aqueous phosphoric acid solution in the first aqueous phosphoric acid solution supply step and The second supply amount of the supply amount of the phosphoric acid aqueous phosphoric acid aqueous solution is supplied to the second step of decision step. The substrate processing method according to claim 1, wherein the first concentration is a value within the predetermined erbium concentration range. The substrate processing method according to claim 1, wherein the second concentration is a value lower than the predetermined erbium concentration range. The substrate processing method of claim 1, wherein the second concentration is zero. The substrate processing method of claim 1, wherein the supply amount determining step In the meantime, the supply amount of the first and second phosphoric acid aqueous solutions is determined such that the concentration of rhodium in the phosphoric acid aqueous solution in the tank is adjusted to a predetermined reference rhodium concentration. The substrate processing method according to claim 1, wherein in the supply amount determining step, the first and second phosphoric acids are determined by setting the target value of the concentration of the cerium concentration in the phosphoric acid aqueous solution in the tank to the first concentration. The amount of supply of the aqueous solution. The substrate processing method according to claim 1, wherein in the supply amount determining step, the supply amount of the first and second phosphoric acid aqueous solutions is determined based on the type of the substrate. The substrate processing method according to claim 1, wherein in the supply amount determining step, the first amount is determined based on an amount of ruthenium eluted from the substrate into the phosphoric acid aqueous solution by the phosphoric acid aqueous solution supplied from the nozzle. And the supply amount of the second phosphoric acid aqueous solution. The substrate processing method according to claim 1, wherein in the supply amount determining step, the first and second factors are determined based on a recovery rate of the phosphoric acid aqueous solution recovered in the tank from the phosphoric acid aqueous solution supplied to the substrate from the nozzle. The amount of the aqueous phosphoric acid solution supplied. The substrate processing method according to claim 1, wherein in the supply amount determining step, the first and second phosphoric acid aqueous solutions are determined based on the number of substrates processed by the phosphoric acid aqueous solution supplied from the nozzle. Supply amount. The substrate processing method of claim 1, wherein the supplementary start condition includes a liquid amount condition relating to a liquid amount stored in the tank. The substrate processing method according to claim 1, wherein the supplementary start condition includes a processing number condition relating to the number of substrates processed by the aqueous phosphoric acid solution supplied from the nozzle. The substrate processing method of claim 1, wherein the supplementary start condition condition package A ruthenium concentration condition relating to the ruthenium concentration in the aqueous phosphoric acid solution supplied from the tank toward the nozzle. The substrate processing method according to claim 1, further comprising a substrate holding step of holding the substrate horizontally, and supplying the phosphoric acid aqueous solution from the nozzle to a surface of the substrate held in the substrate holding step. The substrate processing method according to claim 1, further comprising a third phosphoric acid aqueous solution supply step of including a third concentration different from the first concentration and the second concentration An aqueous phosphoric acid solution is supplied to the above tank. The substrate processing method according to claim 15, wherein the third aqueous phosphoric acid solution supply step is performed in the step of storing the aqueous phosphoric acid solution in the tank, wherein the third concentration is higher than the first concentration. The substrate processing method according to any one of claims 1 to 16, wherein the tank includes a recovery tank into which a phosphoric acid aqueous solution used for substrate processing is introduced via a recovery pipe, and a supply tank through which The phosphoric acid aqueous solution stored in the recovery tank is supplied to the mixing liquid supply pipe, and the phosphoric acid aqueous solution stored in the supply tank is supplied to the nozzle through the supply pipe, and the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution are supplied. To the above recovery tank. The substrate processing method according to claim 17, wherein the plurality of recovery tanks are provided, and the substrate processing method further includes a collection destination selection step of selecting from the plurality of recovery tanks via the recovery piping. Recovered aqueous phosphoric acid solution a destination selection step of selecting a supply destination of the first aqueous phosphoric acid solution and the second aqueous phosphoric acid solution as a recovery tank selected in the collection destination selection step; and a supplementary source selection step The recovery tank not selected in the recovery tank selection step in the plurality of recovery tanks is selected as a supplementary source for replenishing the phosphoric acid aqueous solution to the supply tank via the mixing liquid supply piping. The substrate processing method according to claim 1, further comprising the step of managing the supply amount of the first phosphoric acid aqueous solution in the first phosphoric acid aqueous solution supply step using a first integrated flowmeter; and using the first 2. The step of calculating the supply amount of the second aqueous phosphoric acid solution in the second phosphoric acid aqueous solution supply step by integrating the flow meter. A substrate processing apparatus comprising: a substrate holding means for holding a substrate having a yttrium oxide film and a tantalum nitride film exposed thereon; and a nozzle for supplying a phosphoric acid aqueous solution containing ruthenium to the substrate holding means a substrate; a tank for supplying a phosphoric acid aqueous solution containing a ruthenium having a predetermined ruthenium concentration range to the nozzle; and a recovery pipe for recovering the phosphoric acid aqueous solution used for processing the substrate from the nozzle to the substrate The first aqueous phosphoric acid solution supply means supplies the first aqueous phosphoric acid solution containing ruthenium in the first concentration to the tank, and the second phosphoric acid aqueous solution supply means to the second concentration lower than the first concentration a second aqueous phosphoric acid solution containing ruthenium is supplied to the tank; and a control means for performing a phosphoric acid aqueous solution supply step and a supply amount determining step; and the phosphoric acid aqueous solution supply step is performed by controlling the above-mentioned first when the predetermined supplementary start condition is satisfied The first aqueous phosphoric acid solution and the second aqueous phosphoric acid solution are supplied to the tank by the first aqueous phosphoric acid solution supply means and the second aqueous phosphoric acid solution supply means, and the supply amount determining step determines the supply of the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution. the amount. The substrate processing apparatus according to claim 20, wherein the control means is in the supply amount determining step, based on the type of the substrate, eluted from the substrate to the phosphoric acid aqueous solution by the phosphoric acid aqueous solution supplied from the nozzle. The amount of the phosphoric acid aqueous solution recovered into the tank from the phosphoric acid aqueous solution supplied from the nozzle to the substrate, and the number of substrates processed by the phosphoric acid aqueous solution supplied from the nozzle At least one of them determines the amount of supply of the first aqueous phosphoric acid solution and the second aqueous phosphoric acid solution. The substrate processing apparatus according to claim 20, wherein the supplementary condition includes a liquid amount condition relating to the amount of liquid stored in the tank, and a sheet of the substrate processed by the phosphoric acid aqueous solution supplied from the nozzle The number-related processing number condition and at least one of the enthalpy concentration conditions related to the cerium concentration in the aqueous phosphoric acid solution supplied from the tank toward the nozzle. The substrate processing apparatus according to claim 20, further comprising a third aqueous phosphoric acid solution supply means, wherein the third aqueous phosphoric acid aqueous solution supply means is different from any of the first concentration and the second concentration The third aqueous phosphoric acid solution containing ruthenium is supplied to the tank, and the control means further controls the third aqueous phosphoric acid solution supply means. The substrate processing apparatus according to any one of claims 20 to 23, wherein The present invention includes a recovery tank into which a phosphoric acid aqueous solution used for substrate processing is introduced through a recovery pipe, and a supply tank that is supplied to a phosphoric acid aqueous solution stored in the recovery tank via a mixing liquid supply pipe; The phosphoric acid aqueous solution in the supply tank is supplied to the nozzle through a supply pipe, and the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution are supplied to the recovery tank. The substrate processing apparatus of claim 24, wherein the plurality of recovery tanks are provided, and the control means further performs the following step: a recovery destination selection step of selecting from the plurality of recovery tanks via the recovery piping a collection destination of the recovered phosphoric acid aqueous solution; a supply destination selection step of selecting a supply destination of the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution as the recovery tank selected in the collection destination selection step And a supplementary source selection step of selecting a recovery tank not selected in the recovery tank selection step in the plurality of recovery tanks as a supplement for replenishing the phosphoric acid aqueous solution to the supply tank via the blending liquid supply piping source. The substrate processing apparatus according to claim 20, further comprising: a first integrated flowmeter that measures a supply amount of the first phosphoric acid aqueous solution supplied to the tank by the first phosphoric acid aqueous solution supply means; and a second integrated flowmeter And measuring a supply amount of the second phosphoric acid aqueous solution supplied to the tank by the second aqueous phosphoric acid solution supply means; and the control means further performing a supply amount management step of the supply amount management step The supply of the first phosphoric acid aqueous solution and the second phosphoric acid aqueous solution to the tank is managed based on the measurement results of the first integrated flowmeter and the second integrated flowmeter.