JPH0917766A - Cleaning method of substrate - Google Patents

Abstract

PURPOSE: To obtain a cleaning method in which only a spontaneous oxide film is removed selectively and completely by a method wherein the temperature of a hydrogen fluoride aqueous solution inside a liquid chemical tank is held in a specific range and the pressure in a reaction chamber is held in a specific range. CONSTITUTION: The temperature of the hydrogen fluoride aqueous solution in a liquid chemical tank is held at 0 to 30 deg.C or 30 to 40 deg.C, the vapor of the hydrogen fluoride aqueous solution is generated, the vapor is mixed with the vapor of a solvent for dilution, generated in a solvent tank 22 for dilution, the mixed vapor is introduced into a pressure chamber 10 in which a pressure for vacuum evacuation is held at 80 to 250Torr or 150 to 250Torr, and a spontaneous oxide film on a substrate S is removed. Thereby, only the spontaneous oxide film on the surface of the substrate S can be removed completely, and it can be removed selectively not to affect other coexistent oxide films.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for cleaning a substrate such as a wafer used in a semiconductor device manufacturing process, and more specifically, a substrate such as a wafer is dry-cleaned by using vapor of hydrogen fluoride (HF) aqueous solution. The present invention relates to a method for cleaning a substrate.

[0002]

2. Description of the Related Art In a semiconductor device manufacturing process, cleaning of a wafer is frequently performed because removal of impurities and unnecessary substances on the wafer is important for ensuring performance and yield.

Conventionally, the cleaning of wafers has been carried out exclusively by a process (wet process) in a liquid tank in which the wafer is immersed in a cleaning liquid. However, in wet processing, there are problems such as particles adhering from the cleaning liquid, contamination due to redeposition of impurities, and environmental pollution due to waste liquid. Is being attempted.

As one of the methods, a vapor phase cleaning method using a vapor of a reactive chemical solution such as an aqueous solution of hydrogen fluoride under reduced pressure has been studied.

The process of removing unnecessary substances on a wafer using a chemical vapor such as an aqueous solution of hydrogen fluoride under reduced pressure is considered as follows.

The generated chemical vapor is condensed on the surface of the wafer to be cleaned to form a liquid layer.

In the liquid layer, the same reaction as when the wafer is immersed in the solution occurs. That is, the substance to be removed on the wafer is dissolved or decomposed by this chemical solution.

The reaction product is removed together with the chemical solution and the diluting solvent by evacuation.

[0009]

Prior to forming a film of an electrode material such as tungsten (W) in the step of forming an electrode in a contact hole or forming a film of silicon nitride (SiN) in the step of forming a capacitor, the formation film is formed. It is necessary to remove the native oxide film that causes peeling. When the cleaning method described above is applied to such a step, there are the following problems.

The natural oxide film to be removed has the same chemical composition as the thermal oxide film or the CVD oxide film that constitutes the structure of the device. For this reason, other oxide films coexisting with the natural oxide film on the wafer surface are similarly removed, and defects are caused in the element structure depending on the structure of the element to be manufactured.

Therefore, there is an element having a structure which can be avoided by devising the element structure or by forming the above-mentioned thermal oxide film or the CVD oxide film thick in the preceding step. Complicate the process. In some cases, it is impossible to increase the film thickness of the film exposed on the surface of the structure, such as the side wall portions of the contact hole, the via hole and the trench hole.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for cleaning a substrate such as a wafer that can selectively and completely remove only a natural oxide film.

[0013]

In order to achieve the above object, a method of cleaning a substrate according to the present invention comprises a vapor of a hydrogen fluoride aqueous solution generated in a chemical solution tank of a hydrogen fluoride aqueous solution and a diluting solvent tank. A method of removing the natural oxide film on the substrate by mixing the diluted solvent vapor with the diluted solvent vapor and introducing the diluted solvent vapor into a reaction chamber that has been evacuated, and the temperature of the hydrogen fluoride aqueous solution is 0 to 3
The temperature of the reaction chamber is maintained at 0 to 80 to 250 Torr, or the temperature of the hydrogen fluoride aqueous solution is set to 30 to 40.
It is characterized in that the reaction chamber pressure is maintained at 150 to 250 Torr at 0 ° C.

[0014]

The natural oxide film is relatively thin and has a thickness of at most 5 nm. This means that the amount of removal (etching) is small, which means that the processing time required for removal is short. Therefore, in the removal of such a thin film, the majority of the reaction is the initial process of the removal reaction, that is, the process of forming a liquid layer by condensation of vapor and supplying active species involved in the reaction. That is, in the selective removal of the natural oxide film, it is required that there is a difference in the reaction start time and the removal rate in the initial process.

The pressure of the reaction chamber and the temperature of the aqueous solution of hydrogen fluoride in the chemical tank are important in the formation of the liquid layer in this initial process. The pressure of the reaction chamber changes the thickness of this liquid layer. That is, when the reaction chamber pressure is increased, this liquid layer becomes thicker, and when it is lowered, the liquid layer becomes thinner. The thicker the liquid layer, the closer the situation is to immersion in solution (wet cleaning).

However, since the supply of the active species involved in the reaction and the removal of the reaction product are carried out through the space inside the reaction chamber on the surface of the liquid layer, the situation is not the same as the situation of immersion in the solution.

By increasing the pressure in the reaction chamber, the liquid layer on the surface can be thickened, and the removal rate of the natural oxide film can be increased and complete removal can be performed. On the other hand, if the pressure in the reaction chamber is too high, it becomes difficult to completely remove the native oxide film due to problems of supplying the active species involved in the reaction and removing the reaction products. By maintaining the reaction chamber pressure at 80 to 250 Torr, the natural oxide film can be removed quickly and completely.

The number and status of active species of hydrogen fluoride (HF) in the liquid layer change depending on the temperature of the hydrogen fluoride aqueous solution in the chemical liquid tank. That is, when the temperature of the hydrogen fluoride aqueous solution is lowered, the number of active species is reduced and the activity is reduced.

On the other hand, the natural oxide film and other oxide films such as a thermal oxide film and a CVD film have different film qualities. Therefore, when the temperature of the aqueous hydrogen fluoride solution in the chemical solution tank is lowered, the removal rate and the reaction start time of other oxide films such as the thermal oxide film and the CVD film are changed as compared with the natural oxide film. That is, by setting the temperature of the hydrogen fluoride aqueous solution at 30 ° C. or lower, the reaction start time of another oxide film such as a thermal oxide film or a CVD film is hardly changed with the removal rate of the natural oxide film and the reaction start time. Can be greatly delayed. However, when the temperature of the chemical solution tank is set to 0 ° C or lower, a solvent (ultra pure water) that dilutes hydrogen fluoride (HF) in the chemical solution tank.
Since the vapor pressure of is extremely small, it causes a practical problem.

When the temperature of the hydrogen fluoride aqueous solution in the chemical bath is set to 30 to 40 ° C., the reaction of other oxide films such as a thermal oxide film and a CVD film is smaller than that of 30 ° C. or lower. The start time can be delayed.

Then, the temperature of the hydrogen fluoride aqueous solution in the chemical solution tank is maintained at 0 to 30 ° C., and the reaction chamber pressure is set to 80.
By holding at ~ 250 Torr, it is possible to increase the removal rate of the natural oxide film, delay the reaction start time of other oxide films, and remove only the natural oxide film with almost no removal of other thermal oxide films. it can.

Further, the temperature of the aqueous hydrogen fluoride solution in the chemical solution tank is maintained at 30 to 40 ° C., and the reaction chamber pressure is set to 15
By holding at 0 to 250 Torr, it is possible to remove only the natural oxide film in the same manner without removing other thermal oxide films.

However, when the temperature of the aqueous solution of hydrogen fluoride in the chemical solution tank is kept at 0 to 30 ° C., compared with the case of keeping the temperature of the aqueous solution of hydrogen fluoride in the chemical solution tank at 30 to 40 ° C. Since the delay time of the reaction start time of the other oxide film is long, it is preferable because the processing time can be afforded.

As the diluting solvent, one or more selected from ultrapure water or 2-propanol (isopropyl alcohol, IPA) or the like is used. Inert gas is N ₂ , Ar
And so on.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A substrate cleaning method of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic diagram of the vacuum vapor phase cleaning apparatus used in the test. In the figure, reference numeral 10 denotes a reaction chamber formed of silicon carbide (SiC) or the like and having a substantially hemispherical shape, on which a substrate (wafer) S is arranged. Convex portion 10a formed at the tip of reaction chamber 10
A nozzle 11 for supplying the reactive chemical liquid vapor, the solvent vapor, and the inert gas into the reaction chamber 10 and an exhaust port 12 for exhausting the inside of the reaction chamber 10 are provided therein. The exhaust port 12 is connected by an exhaust path 13 to a vacuum exhaust valve 14 and a vacuum pump 15 whose conductance is variable.

The nozzle 11 is connected to the inert gas supply source 24 via the inert gas supply passage 16, into the chemical liquid tank 19 via the chemical liquid vapor supply passage 18, and into the dilution solvent tank via the solvent vapor supply passage 21. It is connected to 22. Further, in order to control the flow rate thereof, a mass flow controller (hereinafter referred to as M
17, 20 and 23 are provided in the respective supply paths. After the reactive chemical liquid vapor and the diluting solvent vapor are mixed in the mixing section (not shown) of the nozzle 11,
It is supplied from the tip of the nozzle into the reaction chamber.

The chemical liquid tank 19 and the diluting solvent tank 22 are equipped with a heating means (not shown) and a constant temperature holding means (not shown) by a chiller (constant temperature fluid circulation device), respectively. It can be maintained at a predetermined temperature.

In the chemical solution tank 19 and the diluting solvent tank 22, steam is generated at a vapor pressure based on the held temperature, and this is introduced into the reaction chamber by the inert gas through the respective supply passages.

A 38.4% hydrogen fluoride aqueous solution (azeotropic temperature) as a chemical solution, and ultrapure water (resistance value: 1 as a solvent for dilution)
6 MΩ / cm or more) was used. N ₂ was used as the inert gas.

FIG. 2 is a diagram showing a processing sequence of the substrate cleaning method. The vertical axis of FIG. 2 is the change in pressure inside the reaction chamber, and the horizontal axis is the elapsed time.

Pump down: Vacuum exhaust of the reaction chamber removes residual impurities such as air.

Backfill: N ₂ which is an inert gas is introduced into the reaction chamber to raise the pressure in the reaction chamber to the liquid layer forming pressure.

Chemical solution introduction (reaction): A chemical solution vapor of hydrogen fluoride aqueous solution and a solvent vapor for diluting ultrapure water are introduced into the reaction chamber by carrier gas N ₂ . At this time, vacuum evacuation is adjusted so that the pressure is maintained at a predetermined reaction pressure.

Pump down: Evacuate again,
The chemical solution, solvent and reaction product are removed from the substrate surface.

Desorb: Vacuum evacuation is continued for a predetermined time to completely remove the remaining liquid layer and remove the chemical molecules and water adsorbed on the substrate surface.

Backfill: N ₂ which is an inert gas is introduced to raise the pressure of the reaction chamber to the atmospheric pressure, and the substrate can be taken out.

By changing the pressure in the reaction chamber and the temperature of the chemical bath, the time course of the removal (etching) amount of the natural oxide film and the silicon thermal oxide film was measured. The time transition was obtained by changing the time of the chemical introduction (reaction) in the treatment sequence. Other conditions are as follows. Temperature of the solvent tank for dilution: 50 ° C., N ₂ supplied to the chemical solution tank when introducing the chemical solution
Flow rate: 1.0 slm, N ₂ flow rate supplied to the solvent tank for dilution when introducing the chemical solution: 1.0 slm, substrate temperature: room temperature.

For the natural oxide film, one 6-inch silicon wafer is used.
% Hydrofluoric acid (HF) for cleaning, then washing with water, drying and leaving for a predetermined time in a clean room to form. The thermal oxide film was wet-oxidized at 1100 ° C. in an oxidation furnace to give about 10 on a 6-inch silicon wafer.
It was formed to a thickness of 00 nm.

FIG. 3, FIG. 4, FIG. 5 and FIG. 6 are views showing the changes over time in the remaining amount of the natural oxide film and the etching amount of the thermal oxide film. The horizontal axis is the etching time, which is the time for introducing the chemical solution (reaction) in the processing sequence. FIG. 3 shows the result of the reaction chamber pressure: 80 Torr and the chemical solution tank temperature: 50 ° C., and FIG. 4 shows the reaction chamber pressure: 150 Torr, the chemical solution tank temperature:
As a result of 50 ° C., FIG. 5 shows a reaction chamber pressure: 80 Torr, chemical solution tank temperature: 30 ° C., and FIG. 6 shows a reaction chamber pressure: 150 Tor.
rr, chemical bath temperature: 30 ° C. The native oxide film and the thermal oxide film were measured by ellipsometry.

According to these figures, the etching of the natural oxide film starts immediately after the introduction of the chemical, and the etching start time of the thermal oxide film is delayed in comparison with this.

According to the comparison between FIG. 3 and FIG. 4 and FIG. 5 and FIG. 6, by increasing the reaction chamber pressure from 80 Torr to 150 Torr, the etching rate of the natural oxide film increases and the residual amount after a predetermined time. Is decreasing.

According to the comparison between FIG. 3 and FIG. 5 and FIG. 4 and FIG. 6, when the temperature of the chemical bath is lowered from 50 ° C. to 30 ° C., the etching start time of the thermal oxide film is extended from 20 sec to 60 sec. There is.

FIG. 7 is a graph showing the reaction chamber pressure dependence of the remaining amount of the natural oxide film. Remaining amount is etching time 60se
c. At this time, the temperature of the chemical bath was 50 ° C.

When the reaction chamber pressure is increased from 30 Torr, the residual amount first decreases, reaches a minimum value around 150 Torr, and then tends to increase.

Since the residual film thickness is very thin and the measurement error of the ellipsometry method becomes large, it was confirmed by the water repellent test whether the natural oxide film was completely removed and the silicon was exposed on the wafer surface. . As a result, it can be presumed that water repellency was observed on the entire surface of the wafer when the remaining film thickness was 1 nm by the ellipsometry method, and the natural oxide film was completely removed when the remaining amount was 1 nm by the ellipsometry method. That is, from FIG. 7, the reaction chamber pressure is 80 Torr or more and 250 Torr.
It can be said that the natural oxide film was completely removed below.

FIG. 8 is a diagram showing the temperature dependence of the etching amount of the thermal oxide film on the chemical bath temperature. ○ indicates a chemical bath temperature of 30 ° C, △ indicates a chemical bath temperature of 40 ° C, □ indicates a chemical bath temperature of 5
This is the result at 0 ° C. At this time, the reaction chamber pressure is 80 Tor
r. As the temperature of the chemical bath is lowered, the etching rate of the thermal oxide film is reduced and the etching start time is delayed. From this figure, as the temperature of the chemical bath is lowered to 50 ° C, 40 ° C and 30 ° C, the etching start time is 18 sec, 30 sec and 60 sec.
And slow down.

From the above results, the reaction chamber pressure was set to 80 To
By setting the temperature to rr or more and 250 Torr or less and setting the temperature of the chemical bath to 30 ° C. or less, the natural oxide film can be almost selectively etched with respect to the thermal oxide film.

Further, according to FIGS. 4 and 6, if the reaction chamber pressure is set to 150 Torr or more, the etching time is 30
The natural oxide film can be almost completely removed in a time of not less than sec. Therefore, the reaction chamber pressure should be 150 Torr or more and 250To
By setting the temperature to rr or less and setting the temperature of the chemical bath to 40 ° C. or less, the natural oxide film can be etched almost selectively with respect to the thermal oxide film.

In this embodiment, a thermal oxide film is used as another oxide film, but a CVD film or the like can be applied.

[0051]

By using the method for cleaning a substrate of the present invention, it is possible to completely remove only the natural oxide film on the surface of the substrate,
Moreover, selective removal that does not affect other coexisting oxide films becomes possible.

[Brief description of the drawings]

FIG. 1 is a schematic view of a vacuum vapor phase cleaning apparatus used in a test.

FIG. 2 is a diagram showing a processing sequence of a substrate cleaning method.

FIG. 3 is a diagram showing a time transition of a remaining amount of a natural oxide film and an etching amount of a thermal oxide film. Reaction chamber pressure: 80To
rr, chemical bath temperature: 50 ° C.

FIG. 4 is a diagram showing a time transition of a remaining amount of a natural oxide film and an etching amount of a thermal oxide film. Reaction chamber pressure: 150T
orr, chemical bath temperature: when 50 ° C.

FIG. 5 is a diagram showing a time transition of a remaining amount of a natural oxide film and an etching amount of a thermal oxide film. Reaction chamber pressure: 80To
rr, chemical bath temperature: 30 ° C.

FIG. 6 is a diagram showing a time transition of a remaining amount of a natural oxide film and an etching amount of a thermal oxide film. Reaction chamber pressure: 150T
orr, chemical bath temperature: at 30 ° C.

FIG. 7 is a diagram showing the reaction chamber pressure dependency of the remaining amount of a natural oxide film.

FIG. 8 is a diagram showing the temperature dependence of the etching amount of the thermal oxide film on the chemical bath temperature.

[Explanation of symbols]

 10 Reaction Chamber 10a Convex Part 11 Nozzle 12 Exhaust Port 13 Exhaust Channel 14 Vacuum Exhaust Valve 15 Vacuum Pump 16 Inert Gas Supply Channel 17 Mass Flow Controller (MFC) 18 Chemical Vapor Supply Channel 19 Chemical Liquid Tank 20 Mass Flow Controller (MFC) 21 Solvent Vapor Supply path 22 Solvent tank for dilution 23 Mass flow controller (MFC) 24 Inert gas supply source

Claims (1)

[Claims] 1. A mixture of vapor of hydrogen fluoride aqueous solution generated in a chemical solution tank of hydrogen fluoride aqueous solution and diluent solvent vapor generated in a solvent tank for dilution, which is introduced into a reaction chamber evacuated to a vacuum. A method of removing a natural oxide film on a substrate, the temperature of the hydrogen fluoride aqueous solution is kept at 0 to 30 ° C., and the reaction chamber pressure is kept at 80 to 250 Torr, or
A method of cleaning a substrate, characterized in that the temperature of the hydrogen fluoride aqueous solution is maintained at 30 to 40 ° C. and the reaction chamber pressure is maintained at 150 to 250 Torr.