WO1999014801A1

WO1999014801A1 - Method of washing semiconductor substrate and method of producing semiconductor devices using the same method

Info

Publication number: WO1999014801A1
Application number: PCT/JP1998/004134
Authority: WO
Inventors: Katsuhiro Oota; Koji Hara
Original assignee: Hitachi, Ltd.
Priority date: 1997-09-17
Filing date: 1998-09-14
Publication date: 1999-03-25
Also published as: JPH1197406A

Abstract

A method of effectively washing and drying semiconductor substrates having conspicuously rugged and complex surface shapes, and method of producing semiconductor devices with high quality and high yield by using the above method. In washing the substrate having fine grooves of a high aspect ratio such as trench holes formed in the surface, the vapor of a washing solution is fed into the washing chamber, and a saturation vapor pressure or the temperature of the atmoshpere is controlled so that the vapor is condensed on the substrate as a pre-step of washing by the washing solution enabling the washing solution to easily infiltrate into the grooves. Due to the condensation, the washing solution is easily supplied into fine grooves in the semiconductor substrate.

Description

Technical Field Cleaning method of semiconductor substrate and method of manufacturing semiconductor device using the same

The present invention relates to a cleaning method applied to many electronic component manufacturing processes such as electronic materials, magnetic materials, optical materials, and ceramics (hereinafter, a general cleaning method, a surface treatment method, and the like are collectively referred to as a cleaning method). More particularly, the present invention relates to a method for cleaning a semiconductor substrate suitable for a semiconductor device manufacturing process and a method for manufacturing a semiconductor device using the same. Background art

Conventional general cleaning and drying of a semiconductor wafer is performed by immersing the wafer in a cleaning solution such as a diluted hydrofluoric acid or a mixed solution of ammonia and hydrogen peroxide for a predetermined time and then cleaning the wafer with pure water. , Followed by spin drying

1 P A (isopropyl alcohol) This method is used to dry the wafer by vapor drying.

For a mixed solution of ammonia and hydrogen peroxide solution ^ ultrapure water, see, for example, “Silicon Wafer Surface Clean Technology” P. 242 by Takeshi Hattori (published by Realize). For IPA vapor drying, see `` Silicon Wafer Surface Clean Technology ''

285-28 6 Takeshi Hattori, published by Realize, Inc. As another cleaning method, a method in which a semiconductor wafer is immersed in a cleaning liquid in a cleaning tank and the cleaning liquid is vibrated by an ultrasonic generator has been conventionally known (for example, see Japanese Patent Application Laid-Open No. 63-14444). 34 No. 4). This prior art employs a plurality of semiconductor wafers that are immersed in a cleaning solution. An ultrasonic generator is arranged to irradiate the ultrasonic energy beam to the main surface of the wafer so that the ultrasonic energy reaches each surface in the groove.

In recent years, in order to increase the density of integrated circuits, fine deep grooves (width less than lm, depth greater than 5 m) almost perpendicular to the main surface of the semiconductor wafer are processed by dry etching. Attempts have been made to form an element isolation using this groove and to increase the capacity of the capacitor.

In a cleaning means that simply immerses a semiconductor wafer on which a high-density semiconductor integrated circuit having a highly irregular surface and a complex surface shape is formed in a chemical solution and pure water, the chemical solution and pure water are replaced in a deep groove-shaped portion on the surface. Difficult, cleaning effect is significantly reduced.

On the other hand, in order to clean a semiconductor wafer, a method of immersing a semiconductor wafer in a cleaning solution in a cleaning tank and vibrating the cleaning solution with an ultrasonic generator has been conventionally known. JP-A-63-144434 discloses, for example, Japanese Patent Application Laid-Open No. 63-144434 as an effective one for cleaning a semiconductor wafer having been subjected to groove processing. According to this conventional technique, a plurality of ultrasonic generators are arranged so as to surround a semiconductor wafer immersed in a cleaning liquid, and an ultrasonic energy beam is applied to the main surface of the wafer, and each surface of the groove に is illuminated. Ultrasonic energy is applied.

However, with such a cleaning technique, a large number of ultrasonic generators are required to sufficiently clean the grooves of the semiconductor wafer described above. May cause it.

Conventionally, a semiconductor wafer having a sacrificial oxide film formed on the inner surface of a processed groove formed by dry etching was removed by wet etching, so that the semiconductor wafer adhered to the inner surface of the processed groove together with the sacrificial oxide film. Remove contaminants That is being done. However, as described above, since the opening of the groove is fine and deep as described above, the cleaning liquid after the etching liquid is not sufficiently penetrated into the inside of the groove, and a satisfactory inside surface cleaning treatment of the groove must be performed. Could not do.

In addition, even during drying, the moisture present in a complex-shaped portion such as a deep groove-shaped portion such as a crown shape or a fin-shaped stacked structure such as a fin shape is subjected to the spin drying or IPA described above. It is difficult to remove them sufficiently by drying methods such as drying. Insufficient cleaning and drying causes various inconveniences such as deterioration of film quality in subsequent processes such as thin film formation, and has a serious adverse effect on the reliability of integrated circuits.

SUMMARY OF THE INVENTION The present invention has been made in view of such conventional problems, and a method for cleaning a semiconductor substrate capable of effectively cleaning and drying a semiconductor wafer having a complicated surface shape with sharp irregularities. And a method for manufacturing a semiconductor device using the same. Disclosure of the invention

The method for cleaning a semiconductor substrate according to the present invention is characterized in that a cleaning liquid is vaporized in advance and a vapor thereof is condensed on the semiconductor substrate as a pretreatment step of cleaning the semiconductor substrate with a cleaning liquid.

That is, the vapor of the cleaning liquid is supplied onto the semiconductor substrate, and the vapor is condensed (liquefied) on the semiconductor substrate, and then the substrate is cleaned with a predetermined cleaning liquid. This coagulation makes it possible to easily supply the cleaning liquid into the fine grooves of the semiconductor substrate. When cleaning with a cleaning liquid from the beginning, it is difficult to penetrate into these fine grooves because it is a liquid, but it can easily penetrate if it is brought into contact in the state of steam, and it is condensed in the grooves (liquefaction). ), The wettability to the cleaning liquid in the subsequent cleaning process can be increased, and the cleaning with the cleaning liquid can be performed. The effect can be significantly improved.

In order to condense the cleaning liquid, for example, the pressure of the atmosphere filled with the vapor on the semiconductor substrate is raised to a value higher than the saturated vapor pressure of the liquid at the temperature of the atmosphere, or the temperature of the atmosphere becomes the saturated vapor pressure of the liquid. It can be easily carried out by lowering the temperature below the current temperature, or by raising the atmospheric pressure and lowering the temperature.

In the drying process after the cleaning process, reduce the atmospheric pressure to below the saturated vapor pressure of the liquid at that temperature, raise the ambient temperature to a temperature above the saturated vapor pressure of the liquid, or increase the atmospheric pressure. By lowering the temperature and increasing the temperature, the liquid on the semiconductor substrate can be easily evaporated and dried.

The above-mentioned temperature control can be performed in any of the coagulation process and the drying process by (1) the temperature of the atmosphere itself, (2) the temperature of the semiconductor substrate itself placed in the atmosphere, or (3) both of the atmosphere and the semiconductor. That is, one of the temperatures of the substrate is appropriately controlled.

In the present invention, it is also possible to irradiate the liquid with ultrasonic waves during cleaning.

As the cleaning solution, water or a chemical solution is used. Typical examples thereof include an acidic solution containing at least one kind of organic acid including hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, and acetic acid; acidic solution containing at least one of said acidic solution ① and hydrogen peroxide and fluoride Anmoniumu, ③ en Monia water and Amin least ^1: Al force Li solution containing seeds, over and ④ the alkaline solution ③ An alkaline solution containing at least one of hydrogen oxide water and ammonium fluoride, a mixed solution containing an acidic solution of (1) or (2) and an alkaline solution of (3) or (2), or containing water Neutral solutions and the like. Further, the solvent may be an organic solvent. Liquids can be used.

Further, in the above-mentioned washing liquid, a commercially available surfactant such as a cationic surfactant, an anionic surfactant, or an amphoteric surfactant, an organic solvent, or an additive such as a mixture of such a surfactant and an organic solvent is used in combination. You can also.

More specifically, the cleaning liquid used when the cleaning liquid is vaporized in advance and the vapor is condensed on the semiconductor substrate is the same as the cleaning liquid used in the subsequent cleaning step using the liquid. May be different from each other. For example, a typical liquid used to condense the former vapor on a semiconductor substrate is ultrapure water. In any case, these two cleaning solutions may be appropriately selected according to the purpose of cleaning the substrate. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a block diagram of a cleaning method illustrating the basic concept of the present invention, FIG. 2 is a block diagram of another cleaning method illustrating an example of the basic concept of the present invention, and FIG. FIG. 4 is a schematic view schematically showing the infiltration and drying of a cleaning solution into the inside of the fine processing groove, FIG. 4 is a schematic view of a cleaning evaluation sample, and FIG. 5 is a schematic view of a semiconductor device manufacturing process. FIG. 6 is a cross-sectional process diagram of the semiconductor device when the present invention is implemented in the wiring process using A1, and FIG. 6 shows the present invention in the wiring process using Cu in the manufacturing process of the semiconductor device. FIG. 6 is a sectional process view of the semiconductor device when the process is performed. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in more detail with reference to the accompanying drawings.

The outline of the present invention will be described with reference to the basic conceptual diagram shown in FIG. First, as shown in FIG. 1 (a), a semiconductor tank 3 accommodated in a wafer carrier 2 is set in a cleaning tank 1. Then, the steam generator 4 supplies the ultrapure water vapor 6 to the cleaning chamber 5, and then the cleaning chamber 5 is adjusted to an atmospheric pressure equal to or higher than the saturated water vapor pressure of the temperature by the atmospheric pressure adjusting device 7. . Next, as shown in FIG. 1 (b), the cleaning liquid 8 is supplied to the cleaning tank 1 via the cleaning liquid supply device 9 for cleaning. Next, the semiconductor wafer 3 is transferred to the drying chamber 11 by the wafer transfer apparatus 10 and, as shown in FIG. 1 (c), the vapor pressure of the atmosphere is set by the atmosphere pressure adjusting device 7 in the drying chamber. Is reduced to the saturated water vapor pressure or less.

In FIG. 1 (a), the semiconductor wafer 3 housed in the wafer carrier is installed outside the cleaning tank 1 and steam is supplied. After the cleaning liquid is supplied to the cleaning tank 1, the semiconductor wafer 3 is cleaned. Needless to say, it is also possible to perform the washing by immersing in the tank 1.

FIG. 1 shows an embodiment of the present invention. As another cleaning method of the present invention, as shown in FIG. 6 and supply the cleaning chamber 5 with the atmospheric pressure adjusting device 7 so that the atmospheric pressure is equal to or higher than the saturated steam pressure at that temperature, as in the case of FIG. 1 (a). Next, as shown in FIG. 2 (b), the cleaning liquid << is supplied to the cleaning chamber 5 through the cleaning liquid supply device 9 for cleaning. After draining the cleaning liquid, there is also a method in which the atmospheric pressure in the cleaning chamber 5 is reduced to a saturated water vapor pressure or lower, as shown in FIG. 2 (c), and drying is performed.

It should be noted that the order of the steam and the cleaning liquid supplied at the time of cleaning or the order of the steam and the ultrapure water supplied at the time of rinsing as described in the present invention is merely an example. Table 2 shows the order of water vapor and ultrapure water supplied during washing. Item Substance supplied during cleaning

Supplied as vapor as liquid

Number, material supplied Material supplied

1 Ultrapure water washing solution

2 wash

3 Washing solution Washing solution

Further, FIGS. 1 and 2 are merely examples of the present invention, and it goes without saying that the present invention can be applied to a single-wafer cleaning apparatus for cleaning a single wafer, not shown.

According to the present invention, even if a high-aspect ratio structure such as a microfabricated groove 12 is formed on the surface of the semiconductor wafer 3 shown in FIG. At 3 ° C, by raising the atmospheric pressure in the cleaning chamber to 21 T0 rr or more, ultrapure water condenses from steam 6 in the fine processing grooves on the substrate surface, improving wettability. Then, as shown in Fig. 3 (b), When immersed, as shown in FIG. 3 (c), the penetration of the cleaning liquid into the fine grooves is promoted, and as shown in FIG. 3 (d), the cleaning liquid 8 reaches the bottom of the fine processing grooves. You will get enough penetration.

In addition, when the atmospheric pressure in the cleaning chamber 5 is 21 T 0 rr, if the cleaning chamber temperature is lowered to 23 ° C or less without changing the pressure, ultrapure water will be in the fine processing grooves on the substrate surface. Aggregates and improves wettability.

When immersed in the cleaning liquid as shown in FIG. 3 (b), penetration of the cleaning liquid into the fine grooves is promoted as shown in FIG. 3 (c), and as shown in FIG. 3 (d). However, the cleaning liquid sufficiently penetrates to the bottom in the micro-machining groove.

Then, as shown in Fig. 3 (e), after removing the cleaning liquid from the semiconductor wafer, for example, by pulling up the semiconductor wafer from the cleaning liquid or discharging the cleaning liquid from the cleaning tank, the processing proceeds to Fig. 3 (f). As shown in the figure, the inside of the drying chamber is evacuated to about 1 Om Torr and dried. In addition, by performing heating from the back surface of the wafer simultaneously with the pressure reduction, drying can be performed more efficiently.

In the above description, the case where the saturated steam pressure and the temperature are separately controlled has been described. However, it is also possible to perform the cleaning and drying by controlling both of them simultaneously.

According to the present invention, contaminants adhering to the inside of the microfabricated groove can be more reliably removed, and the oxide film can be easily removed at the time of forming the capacitor as described in the section of “Background Art”. A method of cleaning a semiconductor wafer and a method of manufacturing a semiconductor device using the same, which can improve quality and yield, can be realized.

The cleaning effect of the present invention on Fe adsorbed inside the microfabricated groove provided on the wafer was confirmed by the following procedure. Fig. 4 (a) shows a schematic diagram of the cleaning evaluation sample, and Fig. 4 (b) shows a schematic diagram of its cross section. In the cleaning evaluation sample 13, a poly-Si 15 is formed on the Si substrate 14, and a micro-machined groove 12 having an opening diameter of 0.5 im and a depth of 2 μm is formed in the poly-Si. Things.

The following was performed in order to cause the cleaning evaluation wafer 13 to adsorb Fe ions.

Fe ions were added dropwise to a mixed solution of ammonia, hydrogen peroxide and ultrapure water (however, the mixing ratio was adjusted so that the solution had a pH of 11), and the mixture was heated to 50 ° C. Next, the cleaning evaluation wafer was immersed in the mixed solution for 24 hours and washed with water for 20 minutes. Thereafter, the sample was dried for 20 minutes using an IPA vapor drier to prepare a washing evaluation sample 13 to which Fe ions were adsorbed. Then, in order to measure the Fe ions adsorbed on the cleaning evaluation sample, the cleaning evaluation sample was immersed in hot water at 100 ° C for 30 minutes, and the hot water was collected and evaluated with an atomic absorption spectrometer. The residual amount of Fe adsorption in the sample for use was measured.

A cleaning method according to the present invention shown in FIG. 1 (a cleaning step including a pretreatment of a cleaning step of condensing ultrapure water vapor on the wafer) and a conventional method disclosed in, for example, JP-A-63-14434. Washing was carried out by the washing method described above, and both were compared. As the cleaning solution, a mixed cleaning solution of hydrofluoric acid, hydrogen peroxide solution and ultrapure water (however, the mixing ratio was adjusted so that the solution had a pH of 3) was prepared. Table 3 shows the measurement results of the residual amount of Fe adsorption in each of the 25 cleaning evaluation samples cleaned by the present invention and the conventional cleaning method. In the present invention, the value was less than or equal to the lower limit of detection of Fe ion of the measuring device (less than 0.4 ppb) in all samples. However, in the conventional cleaning method, Fe ions were not detected, indicating the superiority of the cleaning effect of the present invention. 0

The present invention was implemented in a general wiring forming process using A1 (for example, described in JP-A-5-3255) in the process of manufacturing a semiconductor device. FIG. 5 shows a schematic diagram of a cross section of the semiconductor substrate. In FIG. 5 (a), reference numeral 14 denotes an Si substrate, 16 denotes an oxide film formed on the surface of the Si substrate 14, 17 denotes an A1 electrode, and 18 to 20 denote interlayer insulating layers. , SiO ₂ film 18 (thickness 200 OA), 3〇0 film 19 (thickness 600 ~: I 20 OA) formed by CVD (chemical vapor deposition) method, formed by CVD method It had a three-layer structure of the obtained SiO ₂ film 20 (film thickness 200 OA). Note that the Si substrate 14 used was a substrate that had been subjected to a cleaning process in advance by the same cleaning method as in Example 1 (a cleaning process including a pre-process of a cleaning process of condensing water vapor of ultrapure water on a wafer). .

As shown in Fig. 5 (a), through holes 21 with a hole diameter of 1.2 μm are formed in the interlayer insulating film layer by dry etching using fluorocarbon CF ₃ , C ₂ F 6, etc. Then, the Al electrode 17 on the semiconductor substrate is exposed. Next, according to the present invention, the semiconductor substrate is supplied with steam at 23 ° C. and 20 T 0 rr, and then washed with a treatment solution composed of an organic alkali solution at 80 ° C. for 15 minutes. By-products shown in Figure (b) 22 was removed. Next, it was washed with water for 20 minutes.

Next, since moisture had penetrated into the through-hole, it was dried in an atmosphere of about 10 mTorr according to the present invention. The A electrodes to expose by through holes Li in this state, generating a thin A 1 ₂ 0 ₃ of any insulator that occurred was not observed in the conventional cleaning method.

Next, an Ar sputtering process is performed.

Furthermore, as shown in FIG. 5 (c), an A 1 wiring layer 17 ′ is formed on the substrate surface including on the A 1 electrode 17 for multilayering, and is patterned to form a wiring connected to the A 1 electrode 17. In the case where is formed, the same procedure as described above may be followed.

After wiring was formed in the above steps, the connection status of each wiring layer was investigated. As a result, it was confirmed that there was almost no contact failure between the wiring layers, and that the contact resistance was extremely small compared to the conventional connection. Therefore, according to the present invention, the defect rate was reduced by 5%, and semiconductors could be manufactured with high quality and high yield.

The present invention was implemented in a general interconnect formation process using CII (for example, described in JP-A-6-326101) in a semiconductor device manufacturing process. Hereinafter, description will be made with reference to the manufacturing process diagram (cross-sectional view) of the semiconductor device shown in FIG.

As shown in FIG. 6A, an insulating film (for example, BPSG film 24 (boron phosphorus phosphorus silicate glass)) is formed on a semiconductor substrate 23 having a diffusion layer and the like (not shown) by a CVD method. Subsequently, a film 25 is formed thereon by sputtering, a TiN film 26 is formed thereon, and a Cu film 27 is further deposited thereon. As explained in Examples 1 and 2, the pre-cleaning process for condensing water vapor on the substrate in advance Used in the cleaning method of the present invention.

Next, as shown in FIG. 6 (b), a resist 28 is applied on the above structure, and patterned by a well-known photolithography and etching technique.

Subsequently, as shown in FIG. 6 (c), the Cu film, the TiN film, and the Ti film are patterned using the resist 28 as a mask. Etch and remove the part other than the part that becomes the wiring.

Next, as shown in FIG. 6 (d), after removing the resist, a mixed cleaning solution of hydrofluoric acid, hydrogen peroxide solution and ultrapure water (however, the mixing ratio is adjusted so that the solution becomes PH = 3). Was washed and dried according to the washing method of the present invention described in Example 1.

Next, the W film 29 covers the wiring portion having the three-layer structure of the Ti film, the TiN film, and the Cu film remaining in the above-described process according to the CVD method shown in FIG.

Next, as shown in FIG. 6 (f), a passivation film 30 (for example, a TiN film) was entirely formed by a CVD method to complete a structure mainly including a wiring portion.

Compared with the conventional cleaning apparatus, the method of manufacturing a semiconductor device to which the cleaning method of the present invention is applied reduces the rejection rate by 5%, and makes it possible to manufacture the semiconductor device with high quality and high yield. Industrial applicability

As described in detail above, the intended object has been achieved by the present invention. In other words, by controlling the saturated vapor pressure and temperature of the atmosphere as a pretreatment step of the cleaning step, the cleaning liquid easily penetrates into the semiconductor wafer having a complicated surface shape with severe irregularities, thereby performing cleaning and drying. It can be performed effectively and can be used for cleaning semiconductor wafers. In addition, the present invention It goes without saying that it can be used not only for cleaning semiconductor wafers, but also for cleaning substrates such as thin film devices and disks.

Claims

A method of cleaning a semiconductor substrate, comprising a step of preliminarily evaporating the cleaning liquid and condensing the vapor on the semiconductor substrate as a pretreatment step before cleaning the semiconductor substrate with the cleaning liquid.

In cleaning a semiconductor substrate with a cleaning liquid, a semiconductor comprising a pretreatment step of vaporizing the cleaning liquid in advance and condensing the vapor into a liquid on the semiconductor substrate; and a cleaning step with the cleaning liquid after the pretreatment step. Substrate cleaning method. The pretreatment step of vaporizing the cleaning liquid and condensing the vapor into a liquid on the semiconductor substrate is performed by increasing the atmospheric pressure in the processing atmosphere to a level higher than the saturated vapor pressure of the liquid at the temperature in the atmosphere. 3. The method for cleaning a semiconductor substrate according to claim 1, wherein said method is a step of coagulating on a semiconductor substrate.

In the pre-treatment process of evaporating the cleaning liquid and condensing the vapor into a liquid on the semiconductor substrate, the liquid in the processing atmosphere is reduced to a temperature below the saturation vapor pressure of the liquid to condense the liquid on the semiconductor substrate. 3. The method for cleaning a semiconductor substrate according to claim 1 or 2, wherein the cleaning is performed as a step.

The pre-treatment process of vaporizing the cleaning liquid and condensing the vapor into a liquid on the semiconductor substrate is performed by raising the atmospheric pressure in the processing atmosphere to a value higher than the saturated vapor pressure of the liquid at the temperature in the atmosphere and raising the temperature to liquid. Controlling the saturated vapor pressure and temperature in the processing atmosphere to condense the vapor to liquid on the substrate by lowering the temperature below the temperature at which the saturated vapor pressure is reached. 3. The method for cleaning a semiconductor substrate according to claim 1 or 2, wherein the cleaning is performed.

Claims 1 to 5 further comprising, after the cleaning step, a drying step of removing the liquid from the semiconductor substrate by lowering the atmospheric pressure in the processing atmosphere to a value lower than the saturated vapor pressure of the liquid at the temperature in the processing atmosphere. Described in any one of A method for cleaning a semiconductor substrate.

The method according to any one of claims 1 to 5, further comprising, after the cleaning step, a drying step of removing the liquid from the semiconductor substrate by increasing the temperature in the processing atmosphere to a temperature or higher at which the saturated vapor pressure of the liquid is reached. A method for cleaning a semiconductor substrate according to one aspect.

After the cleaning process, the atmospheric pressure in the processing atmosphere is reduced below the saturated vapor pressure of the liquid at the temperature in the atmosphere, and the temperature in the processing atmosphere is raised above the temperature at which the saturated vapor pressure of the liquid is reached. 6. The method for cleaning a semiconductor substrate according to claim 1, further comprising a drying step of removing a liquid from the semiconductor substrate.

9. The method for cleaning a semiconductor substrate according to any one of claims 1 to 8, wherein a step of irradiating the cleaning liquid with ultrasonic waves in the cleaning step is added.

10. The method for cleaning a semiconductor substrate according to any one of claims 1 to 9, wherein the cleaning liquid comprises water or a chemical solution.

1 1. The cleaning solution is composed of ① an acidic solution containing at least one kind of organic acid including hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, ② the acidic solution ②, hydrogen peroxide solution and ammonium fluoride. An acidic solution containing at least one of the following: ③ an alkaline solution containing ammonia water and at least one of amines; ④ an alkaline solution containing the alkaline solution ③ and at least one of hydrogen peroxide solution and ammonium fluoride; 10. The semiconductor according to any one of claims 1 to 9, comprising a mixed solution containing the acidic solution of (1) or (2) and the alkaline solution of (3) or (2), or (2) a neutral solution containing water. Substrate cleaning method.

12. The method for cleaning a semiconductor substrate according to any one of claims 1 to 9, wherein the cleaning liquid comprises an organic solvent.

13 3. Add at least one of surfactant and organic solvent to the cleaning solution 10. The method for cleaning a semiconductor substrate according to any one of claims 1 to 9, wherein the semiconductor substrate is contained.

4. The method for cleaning a semiconductor substrate according to claim 13, wherein the surfactant comprises at least one of a cationic surfactant, an anionic surfactant and an amphoteric surfactant.

5. A method for manufacturing a semiconductor device having at least a semiconductor substrate cleaning step, wherein the cleaning step is constituted by the semiconductor substrate cleaning method according to any one of claims 1 to 14. Manufacturing method.