# Patent

## Title
Cleaning solution for a semiconductor wafer

## Abstract

A cleaning solution for a semiconductor wafer comprises ammonia, hydrogen peroxide, a complexing agent and a block copolymer surfactant diluted in water. The cleaning solution can be used in single wafer cleaning tools to remove both particulate contaminants and metallic residues.

## Background
FIELD OF THE INVENTION
This invention relates to a cleaning solution of the type, for example, that removes particulate contaminants organic and/or metallic residues from a surface of a semiconductor wafer.
BACKGROUND OF THE INVENTION
In the field of semiconductor wafer manufacturing, it is necessary for a wafer to undergo a so-called “wet clean” processing stage prior to patterning of gates. This processing stage is an important stage in the manufacture of semiconductor wafers, because cleanliness of the surface of the wafer at this early stage of manufacture impacts upon defectivity and hence yields of semiconductor devices ultimately made.
Historically, the wet clean stage comprises two cleaning step. Using a first wet bench, a first step requires wafers to undergo a so-called “RCA clean” using a Standard Clean 1 (SC-1) cleaning solution. The SC-1 cleaning solution has an alkaline pH and comprises ammonia, hydrogen peroxide and water. After the RCA clean, a second step of the wet clean stage employs a second wet bench to immerse the wafers in a Standard Clean 2 (SC-2) cleaning solution comprising hydrochloric acid, hydrogen peroxide and water, the SC-2 cleaning solution having an acid pH.
The SC-1 cleaning solution is highly efficient at removing particles and organic residuals, due to a high Zeta potential in the alkaline range of dielectric surfaces commonly forming part of a surface of a semiconductor wafer. However, the SC-1 cleaning solution is ineffective at removing metallic contamination, such as residues. The second, acidic, clean part of the wet clean stage using the SC-2 cleaning solution is therefore necessary, and use of the wet benches moreover allows batch cleaning of semiconductor wafers.
Wafer sizes are now changing and a migration to 300 mm diameter wafers is taking place. A necessary result of the migration to the 300 mm wafer size is the replacement of the above-described wet benches with single wafer processing tools to avoid cross contamination between wafers being cleaned simultaneously in a given wet bench. This change to single wafer processing tools to wet clean the wafers poses a new challenge to users of the wet clean step, since in order to maintain the throughput of wafers in the wet clean step, each individual wafer has to be cleaned in about 30 seconds as opposed to the 10 minutes taken previously when the wafers were batch cleaned. In order to facilitate the reduced process time per wafer required, it is desirable to combine the functions of the alkaline and the acidic cleaning steps.
U.S. Pat. Nos. 6,143,706, 6,228,179, 6,228,823 and 6,498,132 disclose possible cleaning solutions to reduce the cleaning time of wafers in the single wafer processing tools. The cleaning solutions disclosed operate in the alkaline range of pH to remove particulate contaminants with high efficiency. Efficiency of removal of metallic residues is addressed by employing a variety of complexing agents in the cleaning solution, the complexing agents typically containing ethylene-diamine and derivatives thereof.
Whilst the above-mentioned cleaning solutions show promise for several cleaning applications, in cleaning stages where efficiency of metal removal is critical, the above-mentioned cleaning solutions do not always provide sufficient cleaning efficiency for some applications to avoid compromising the (Charge-to-Breakdown) reliability of devices being formed.
It is, of course, known that removal of metallic species in alkaline media is difficult due to low solubility of the metallic species in the alkaline media and the high affinity of the metallic species to surface silanol groups at high pH. Removal of the metallic species is therefore driven by completing agents, though the complexing agents have to be highly efficient in order to remove the metallic species from the surface of the wafer in such a short processing time. In order to improve the efficiency of removal of the metallic species, U.S. Pat. No. 6,498,132 therefore proposes the use of multiple complexing agents.
However, even with the use of multiple complexing agents, removal of metallic species from the surfaces of wafers is still inefficient. Prior to the wet clean stage, the surface of a semiconductor wafer is hydrogen terminated, resulting in the surface of the wafer being hydrophobic. When cleaned in an alkali media, silicon on a surface of the semiconductor wafer undergoes oxidation resulting in the surface of the semiconductor wafer acquiring hydrophylic wetting properties. Consequently, the accessibility of the complexing agents to surface sites of the wafers is hindered by the inhomogeneous wet-ability of the surface of the semiconductor wafer during the oxidation of the silicon.
STATEMENT OF INVENTION
According to the present invention, there is provided a cleaning solution as set forth in the appended claims.



BRIEF DESCRIPTION OF THE DRAWINGS
At least one embodiment of the invention will now be described, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a first surfactant molecule for use in a cleaning solution constituting a first embodiment of the invention;
FIG. 2 is a schematic diagram of a second surfactant molecule for use in a cleaning solution constituting a second embodiment of the invention; and
FIG. 3 is a schematic diagram of a third surfactant molecule for use in a cleaning solution constituting a third embodiment of the invention.



DESCRIPTION OF PREFERRED EMBODIMENTS
A wafer cleaning apparatus (not shown) or tool comprises a bath in which a cleaning solution is introduced via an inlet port. Semiconductor wafers (not shown) are subsequently, and individually, immersed in the cleaning solution prior to a gate patterning stage. The cleaning process does not differ from known cleaning processes used to clean semiconductor wafers individually prior to gate patterning and so, for the sake of conciseness and simplicity of description, will not be described further herein.
The cleaning solution is made by adding ammonia, a complexing agent, hydrogen peroxide, and a block polymer surfactant to water, such that the mixture on the surface of the wafer comprises the above components in the following proportions. The mixture comprises between about 0.01 wt % and about 0.1 wt % of ammonia, between about 0.01 wt % and about 0.2 wt % of hydrogen peroxide, less than about 0.1 wt % of the complexing agent, and less than about 0.01 wt % of the block polymer surfactant. The remainder of the mixture is water; in this example, de-ionised water is employed. Of course, different ranges of proportions of components can be employed, for example. The concentration of the components can be changed and tailored to individual equipment. For example, the concentration of ammonia and hydrogen peroxide can be less than 5 wt %, the concentration of complexing agents can be less than 3 wt %, and the concentration of the block polymer surfactant can be less than 1 wt %.
The ammonia is an example of an alkaline used, but the skilled person will appreciate that other alkalines having a pH greater than 8 can be used, for example a pH greater than 9, such as a pH greater than 10.
Referring to FIGS. 1 and 2, the block polymer is, in this example, a linear block polymer surfactants, such as a normal or reverse Pluronics® surfactant available from BASF. In this example (FIG. 1), the Pluronics surfactant used is a triblock copolymer of two hydrophobic polypropylene oxide (PO) groups or chains connected by a hydrophilic polyethylene oxide (EO) group or chain, or vice versa for the reverse type (FIG. 2). Of course, other block polymers available from different vendors, such as Clariant, can, alternatively, be used.
As already explained above, silicon on the surface of semiconductor wafers is hydrogen terminated prior to cleaning and so is hydrophobic. However, as a result of exposure to the high pH medium for removal of particulate contaminants from the surface of the semiconductor wafer, the silicon is oxidised yielding hydrophilic wetting properties. Since the PO chain of Pluronics interacts with hydrophobic surfaces, the PO chain serves as a wetting agent to allow the complexing agent to access the surface sites where metallic residues are present. Consequently, the efficiency of the reaction of the complexing agent with the metallic residues on the surface of the semiconductor wafers is improved, resulting in improved removal of the residues.
In another embodiment (FIG. 3), the linear block polymer surfactant is a normal and reverse Tetronic® surfactant available from BASF. Tetronics are tetrafunctional copolymers of two hydrophobic polypropylene oxide (PO) hydrophilic groups or chains connected by a polyethylene oxide (EO) group or chain.
Although particular examples of block copolymer surfactants have been described above, the skilled person will appreciate that different surfactants having different molecular weights comprising different ratios of PO to EO groups can be used to achieve different wetting properties depending upon a particular cleaning application to be carried out. Typically, the molecular weight of the surfactant is between about 1500 and about 15000 mwu, and the EO:PO ratio can be from 1:10 to 1:1.
Although the above mixtures have been described in their respective dilute forms, the skilled person will appreciate that the cleaning solutions can be provided in concentrated forms of between about 10× and about 100× concentrate for dilution in de-ionised water prior to use.
It is thus possible to provide a cleaning solution that is capable of wetting both hydrophobic and hydrophilic surfaces homogenously. Consequently, accessibility by the complexing agents to a surface of a wafer is improved. The cleaning solution therefore reacts more homogeneously with the surface of the wafer than other known cleaning solutions, resulting in improved efficiency of material removal from the surface. Since, the length and ratio of the hydrophilic and hydrophobic groups can also be modified easily, thereby enabling the surfactant to be tailored to specific chemistries for different cleaning applications. Additionally, block polymers do not result in the formation of micelles and so are not sensitive to precipitation.

## Claims

1. A cleaning solution for removal of particulate contaminants and metallic residues from a surface of a semiconductor wafer, the solution comprising:
an alkali;
hydrogen peroxide;
water;
a complexing agent; and
a surfactant in an amount of less than 1 wt %; wherein the surfactant is a triblock copolymer type surfactant having at least one hydrophilic copolymer block and at least one hydrophobic copolymer block.

2. A solution as claimed in claim 1, wherein the hydrophobic copolymer block includes a polypropylene oxide group and the hydrophilic copolymer block includes a polyethylene oxide group.

3. A solution as claimed in claim 2 wherein the ratio of the polyethylene oxide groups to the polypropylene oxide groups is between 1:10 to 1 :1.

4. A solution as claimed in claim 1 wherein the block copolymer
type surfactant has a molecular weight of between about 1500 and about 15000 mwu.

5. A solution as claimed in claim 1 wherein the solution comprises between about 0.01 wt % and about 5 wt % of the alkali.

6. A solution as claimed in claim 1 wherein the solution comprises between about 0.01 wt % and about 5 wt % of hydrogen peroxide.

7. A solution as claimed in claim 1 wherein the solution comprises less than about 3 wt % of the complexing agent.

8. A method comprising:
cleaning using a cleaning solution, the cleaning solution including:
an alkali;
hydrogen peroxide;
water;
a complexing agent; and
a surfactant in an amount less than 1 wt %; wherein the surfactant is a triblock copolymer type surfactant having at least one hydrophilic copolymer block and at least one hydrophobic copolymer block.

9. A method comprising:
cleaning a semiconductor wafer using a cleaning solution, the cleaning solution including:
an alkali;
hydrogen peroxide;
water;
a complexing agent; and
a surfactant; wherein the surfactant is a triblock copolymer type surfactant having at least one hydrophilic copolymer block at least one hydrophobic copolymer block.

10. A method as claimed in claim 9, wherein the hydrophobic copolymer block includes a polypropylene oxide group and the hydrophilic copolymer block includes a polyethylene oxide group.

11. A method as claimed in claim 10 wherein the ratio of the polyethylene oxide groups to the polypropylene oxide groups is between 1:10 to 1:1.

12. A method as claimed in claim 9 wherein the surfactant is the triblock copolymer having two of the at least one hydrophobic copolymer blocks connected by the at least one hydrophilic copolymer block.

13. A method as claimed in claim 9 wherein the surfactant is the triblock copolymer having two polypropylene oxide copolymer blocks connected by a polyethylene oxide copolymer block.

14. A method as claimed in claim 9 wherein the cleaning solution includes less than 1 wt % of the surfactant.

15. A method as claimed in claim 9 further comprising patterning gates, wherein cleaning the semiconductor wafer is performed prior to patterning gates.

16. A cleaning solution as claimed in claim 1 wherein the alkali includes ammonium hydroxide.

17. A cleaning solution as claimed in claim 6 wherein the solution comprises between about 0.01 wt % and about 0.2 wt % of the hydrogen peroxide.

18. A cleaning solution as claimed in claim 1 wherein the solution has a pH of at least 8.

19. A cleaning solution as claimed in claim 18 wherein the solution has a pH of at least 9.

20. A cleaning solution as claimed in claim 1 wherein the triblock copolymer includes two polypropylene oxide copolymer blocks connected by a polyethylene oxide copolymer block.