CN109427543A - The washing methods of silicon wafer - Google Patents
The washing methods of silicon wafer Download PDFInfo
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- CN109427543A CN109427543A CN201710769387.0A CN201710769387A CN109427543A CN 109427543 A CN109427543 A CN 109427543A CN 201710769387 A CN201710769387 A CN 201710769387A CN 109427543 A CN109427543 A CN 109427543A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
Abstract
The washing methods of silicon wafer of the invention is characterized in that having the process for successively impregnating silicon wafer: (1) being impregnated in dissolved ozone aqueous solution etc.；(2) it is impregnated in the aqueous solution comprising hydrogen peroxide and ammonium hydroxide；(3) it is impregnated in dissolved ozone aqueous solution etc.；(4) it is impregnated in the aqueous solution comprising organic acid or acylate and hydrofluoric acid with carboxyl；(5) it is impregnated in the aqueous solution comprising the organic acid containing carboxyl or acylate；(6) it is impregnated in pure water；And (7) are impregnated in dissolved ozone aqueous solution etc..It can not only reduce by 0.1 μm of partial size or more of big particle as a result, but also the particle that 0.045 μm of partial size small particle and partial size below are more than 0.045 μm and the intermediate sizes less than 0.1 μm can be reduced.
Description
Technical field
The present invention relates to the washing methods of silicon wafer.
Background technique
On the surface of silicon wafer, adhesion metal impurity, partial size are 1 μm of particle below and organic in its manufacturing process
Object etc., and form machining damage.Along with highly integrated, the multifunction of semiconductor devices, the surface of silicon wafer is increasingly required
Not by these metal impurities, particle and organic pollution, and without machining damage, the washing technology for meeting the silicon wafer of this requirement exists
Become of crucial importance among semiconductor device art entirety.
The washing methods of the silicon wafer with following processes is described in patent document 1: by silicon wafer be impregnated in comprising
Process (11) in the aqueous solution (so-called SC-1 solution) of hydrogen oxide and ammonium hydroxide；Thereafter, aforementioned silicon wafer is impregnated in
Include the process in the one kind or two or more oxidation solution selected from dissolved ozone aqueous solution, nitric acid and aqueous hydrogen peroxide solution
(12)；Thereafter, aforementioned silicon wafer is impregnated in the aqueous solution comprising organic acid or acylate and hydrofluoric acid with carboxyl
Process (13)；Thereafter, aforementioned silicon wafer is impregnated in the aqueous solution comprising the organic acid containing carboxyl or acylate
Process (14)；Thereafter, aforementioned silicon wafer is impregnated in comprising selected from dissolved ozone aqueous solution, nitric acid and aqueous hydrogen peroxide solution
Process (15) in one kind or two or more oxidation solution.It, can be with less process number and good it is said that according to the washing methods
Ground removes the microlesion generated due to processing, and is attached to the organic matter, metal impurities and particle of silicon wafer surface.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2000-138198 bulletin.
Summary of the invention
Problems to be solved by the invention
In patent document 1, it in embodiment, is had rated using particle collector and remains on the silicon wafer surface after washing
The number of 0.12 μm of partial size or more the particle of size.Moreover, showing can be effectively according to the washing methods of patent document 1
It removes, reduce this biggish particle.
But in patent document 1, the smaller particle about partial size less than 0.12 μm, does not carry out any consideration
And evaluation.In the case where the highly integrated of semiconductor devices, multifunction, it is desirable that be also effectively removed washing for small particle
It washs.Therefore, present inventor has performed research and experiment, distinguish: although can have really in the washing methods of patent document 1
The removal of effect ground, the big particle for reducing 0.1 μm of partial size or more, but about 0.045 μm of partial size small particle and partial size below
More than 0.045 μm and the particle of the intermediate sizes less than 0.1 μm, then remove, the effect of reduction it is insufficient.
Therefore, the present invention in view of the above subject, and it is an object of the present invention to provide: can not only reduce by 0.1 μm of partial size or more big
Particle, and can reduce by 0.045 μm of partial size small particle and partial size below is more than 0.045 μm and less than in 0.1 μm
Between size particle silicon wafer washing methods.
Means for solving the problems
The present inventor furthers investigate to reach above-mentioned purpose, obtains opinion below.Firstly, in patent document 1
Washing methods in, inventors believe that following 2 points the reason of may be the particle more residual of small particle and intermediate sizes:
(A) the organic matter removal effect of the washing procedure (11) carried out by SC-1 solution there are it is insufficient a possibility that；(B) in process
(13) and after process (14), there is a possibility that residual organic acid in silicon wafer surface.
Therefore, the countermeasure as (A), it is contemplated to: before the process of the washing procedure (11) carried out by SC-1 solution,
The additional washing procedure being impregnated in silicon wafer in the oxidation solution of dissolved ozone aqueous solution etc., removes silicon by the washing procedure
The organic matter of wafer surface.In addition, the countermeasure as (B), it is contemplated to: immediately following after process (14), addition impregnates silicon wafer
Washing procedure in pure water removes remaining organic acid by the washing procedure.Moreover, people tests according to the present invention
Know, by above-mentioned 2 washing procedures of addition, the particle of small particle and intermediate sizes can be effectively removed.
And it is especially surprising that learning: the oxidation solution about the particle of intermediate sizes, before additional washing procedure (11)
Washing procedure and the additional washing procedure immediately following the pure water after process (14) among, when only carrying out any one, intermediate sizes
Particle removal effect it is insufficient, in contrast, by carry out both, promoted significantly the particle of intermediate sizes removal effect
Fruit.
The present invention is completed based on above-mentioned opinion, and main idea constitutes as follows.
(1) washing methods of silicon wafer, which is characterized in that there is following processes:
Silicon wafer is impregnated in comprising a kind or 2 selected from dissolved ozone aqueous solution, nitric acid and aqueous hydrogen peroxide solution by the 1st process
Kind or more the 1st oxidation solution in；
Aforementioned silicon wafer after aforementioned 1st process, is impregnated in the aqueous solution comprising hydrogen peroxide and ammonium hydroxide by the 2nd process
In；
After aforementioned 2nd process, aforementioned silicon wafer is impregnated in comprising selected from dissolved ozone aqueous solution, nitric acid and mistake for 3rd process
In the 2nd one kind or two or more oxidation solution for aoxidizing aqueous solution of hydrogen；
After aforementioned 3rd process, aforementioned silicon wafer is impregnated in comprising organic acid or acylate with carboxyl for 4th process
And in the aqueous solution of hydrofluoric acid；
After aforementioned 4th process, aforementioned silicon wafer is impregnated in comprising organic acid or acylate containing carboxyl for 5th process
Aqueous solution in；
After aforementioned 5th process, aforementioned silicon wafer is impregnated in pure water for 6th process；And
After aforementioned 6th process, aforementioned silicon wafer is impregnated in comprising selected from dissolved ozone aqueous solution, nitric acid and mistake for 7th process
In the 3rd one kind or two or more oxidation solution for aoxidizing aqueous solution of hydrogen.
(2) washing methods of silicon wafer described in above-mentioned (1), wherein aforementioned 1st oxidation solution, aforementioned 2nd oxidation solution and
Aforementioned 3rd oxidation solution is respectively the 1st~the 3rd dissolved ozone aqueous solution.
(3) washing methods of silicon wafer described in above-mentioned (2), wherein in aforementioned 1st and the 2nd dissolved ozone aqueous solution
Ozone concentration be 5ppm or more and 10ppm hereinafter, the ozone concentration in aforementioned 3rd dissolved ozone aqueous solution be 15ppm or more and
30ppm or less.
(4) washing methods of described in any item silicon wafers of above-mentioned (1)~(3), wherein used in aforementioned 4th process
Aqueous solution in hydrofluoric acid concentration be 0.05 mass % or more and 1.0 mass % or less.
(5) washing methods of described in any item silicon wafers of above-mentioned (1)~(4), wherein aforementioned 4th process and aforementioned
The concentration of organic acid or acylate in aqueous solution used in 5th process is 0.001 mass % or more.
(6) washing methods of described in any item silicon wafers of above-mentioned (1)~(5), wherein aforementioned organic acid is organic
Hydrochlorate is one kind or two or more organic acid selected from the following or its salt: oxalic acid, citric acid, succinic acid, ethylenediamine tetra-acetic acid, wine
Stone acid, salicylic acid, formic acid, maleic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, benzoic acid, acrylic acid, oneself two
Acid, malonic acid, malic acid, glycolic, phthalic acid, terephthalic acid (TPA) and fumaric acid.
Invention effect
The washing methods of silicon wafer according to the present invention can not only reduce 0.1 μm of partial size or more of big particle, Er Qieke
To reduce the particle that 0.045 μm of partial size small reliably partial size below is more than 0.045 μm and the intermediate sizes less than 0.1 μm.
Detailed description of the invention
Fig. 1 is the flow chart for showing each process of the washing methods of silicon wafer of an embodiment of the invention.
Specific embodiment
Hereinafter, side is referring to Fig.1, while being illustrated to the washing methods of the silicon wafer of an embodiment of the invention.This
The washing methods of embodiment is not that single wafer is washed as the final washing before the silicon wafer delivery for completing finished product grinding
It washs but batch washing can be appropriate for.
(the 1st process)
Firstly, be impregnated in silicon wafer comprising selected from dissolved ozone aqueous solution, nitric acid and peroxidating as shown in the S1 of Fig. 1
The 1st process in the 1st one kind or two or more oxidation solution of aqueous solution of hydrogen.In the 1st process S1, silicon wafer surface will be attached to
Organic fine particles etc. be removed by chemical oxidation effect.Especially since ozone has stronger organic matter capacity of decomposition,
Therefore advantageously when removal is attached to the organic fine particles etc. of wafer surface.Therefore, the 1st oxidation solution is preferably dissolved ozone water
Solution.It for efficiently reducing partial size is more than 0.045 μm and less than in 0.1 μm that 1st process, which is with aftermentioned 6th process step combinations,
Between size particle important procedure.
Ozone concentration in dissolved ozone aqueous solution is preferably 5ppm or more and 10ppm or less.Ozone concentration be 5ppm with
When upper, function and effect required described in previous paragraphs can be fully obtained, when ozone concentration is 10ppm or less, without high price
Ozone generating-device, be advantageous in terms of cost.
Dip time in this process is not particularly limited, preferably 3 minutes or more and 10 minutes or less.By being 3
Minute or more, above-mentioned required function and effect can be fully obtained, by imitating for 10 minutes hereinafter, washing will not be undermined
Rate.The temperature of 1st oxidation solution is not particularly limited, such as can be for 15 DEG C or more and 30 DEG C hereinafter, typically can be
Room temperature (25 DEG C).
(the 2nd process)
Secondly, be impregnated in silicon wafer the aqueous solution (SC-1 comprising hydrogen peroxide and ammonium hydroxide as shown in the S2 of Fig. 1
Solution) in the 2nd process.In the 2nd process S2, reduction based on ammonia and competed in same slot based on the oxidation of hydrogen peroxide
Occur, silicon wafer surface receives to aoxidize simultaneously and restore, and can be effectively removed the small of the number ran thickness of wafer surface
Damaging layer.In addition, by the etching action of Ammonia particle and organic matter can be removed from wafer surface, and can remove
The microlesion generated on chip due to processing.The washing of 2nd process is preferably carried out by supersound washing.Thus, it is possible to
The washing reduced in wafer surface is uneven.
It is molten in common SC-1 for the concentration of hydrogen peroxide and ammonium hydroxide concentration in aqueous solution used in this process
In the range of liquid, specifically, concentration of hydrogen peroxide can be 1.5~4.0 mass %, ammonium hydroxide concentration can be
0.3~2.0 mass %.
Dip time in this process is not particularly limited, preferably 3 minutes or more and 10 minutes or less.By being 3
Minute or more, above-mentioned required function and effect can be fully obtained, by imitating for 10 minutes hereinafter, washing will not be undermined
Rate.The temperature of aqueous solution is not particularly limited, preferably 40 DEG C or more and 80 DEG C or less.This is because, when being 40 DEG C or more,
It can fully ensure particle removal ability, when being 80 DEG C or less, the surface roughness of wafer surface will not become excessively coarse.
(the 3rd process)
In the SC-1 solution processing of the 2nd process, there is the situation adhered to again for causing metal impurities and particle.Therefore, secondly,
As shown in the S3 of Fig. 1, silicon wafer is impregnated in comprising selected from dissolved ozone aqueous solution, nitric acid and aqueous hydrogen peroxide solution
The 3rd process in the 2nd one kind or two or more oxidation solution.In the 3rd process S3, make to be formed by oxidation film after the 2nd process
Density by chemical oxidation act on further promoted, thus in next 4th process, by the way that the oxidation film is dissolved
Metal impurities and particle are made to be easy to be detached from from wafer surface.In particular, dissolved ozone aqueous solution is at low concentrations rich in energy of oxidation
Power and easy acquisition.Therefore, the 2nd oxidation solution is preferably dissolved ozone aqueous solution.
Ozone concentration in dissolved ozone aqueous solution is preferably 5ppm or more and 10ppm or less.Ozone concentration be 5ppm with
When upper, function and effect required described in previous paragraphs can be fully obtained, when ozone concentration is 10ppm or less, without high price
Ozone generating-device, be advantageous in terms of cost.
Dip time in this process is not particularly limited, preferably 3 minutes or more and 10 minutes or less.By being 3
Minute or more, above-mentioned required function and effect can be fully obtained, by imitating for 10 minutes hereinafter, washing will not be undermined
Rate.The temperature of 2nd oxidation solution is not particularly limited, such as can be for 15 DEG C or more and 30 DEG C hereinafter, typically can be
Room temperature (25 DEG C).
(the 4th process)
Secondly, be impregnated in silicon wafer comprising organic acid or acylate and hydrogen fluorine with carboxyl as shown in the S4 of Fig. 1
The 4th process in the aqueous solution of acid.In the 4th process S4, make the metal being incorporated into oxidation film in the 2nd process and the 3rd process
Impurity and particle are detached from and dissolving oxidation film from wafer surface.Specifically, it is believed that cause following phenomenon.Firstly,
Hydrofluoric acid dissolution oxidation film fully removes oxidation film wafer surface.Metal impurities and particle are detached from it from wafer surface
Afterwards, which immediately passes through organic acid ion and forms metallic complex salt.The complex ion of the metallic complex salt is anion.
In addition, eliminating the wafer surface of oxidation film and the surface of particle that has disengaged from is due to Adsorption organic acid ion and with negative
Charge.As a result, metal impurities and particle can be prevented to be attached to wafer surface again.
By changing the type and concentration of organic acid or acylate, the metal complex based on organic acid ion can control
Change the surface potential (zeta potential) of effect and metallic complex salt.That is, the complex compound Forming ability of organic acid ion according to organic acid from
Son with formation complex compound metal ion Complex Stability Constants and chemically determine.The constant is bigger, then can more promote network
Ion is closed to be formed.As previously mentioned, by forming complex ion, the charge of metal ion changes from positive to bear.
The type and concentration of organic acid or acylate in aqueous solution used in this process, according to the gold to be removed
Belong to the type of impurity and determines.The concentration of organic acid or acylate is preferably 0.001 mass % or more, and more preferably 0.003
~10 mass %.By the way that for 0.001 mass % or more, the complexing of the metal impurities ion to dissociate from wafer surface becomes to fill
Point.
As organic acid used in this process or acylate, can enumerate selected from the following one kind or two or more organic
Acid or its salt: oxalic acid, citric acid, succinic acid, ethylenediamine tetra-acetic acid, tartaric acid, salicylic acid, formic acid, maleic acid, acetic acid, propionic acid,
Butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, benzoic acid, acrylic acid, adipic acid, malonic acid, malic acid, glycolic, O-phthalic
Acid, terephthalic acid (TPA) and fumaric acid.The above-mentioned organic acid enumerated or acylate have the metal ion of the impurity of pollution chip
There is complexing.
The concentration of hydrofluoric acid in aqueous solution used in this process be preferably 0.05 mass % or more and 1.0 mass % with
Under, more preferably 0.1 mass % or more and 0.5 mass % or less.By the way that crystalline substance can be obtained fully for 0.05 mass % or more
The release effect of the natural oxide film on piece surface, by for 1.0 mass % hereinafter, being difficult to cause adhering to again for particle in liquid.
Dip time in this process is not particularly limited, preferably 3 minutes or more and 10 minutes or less.By being 3
Minute or more, above-mentioned required function and effect can be fully obtained, by imitating for 10 minutes hereinafter, washing will not be undermined
Rate.The temperature of aqueous solution is not particularly limited, such as can be for 15 DEG C or more and 30 DEG C hereinafter, typically can be room temperature
(25℃)。
(the 5th process)
Secondly, as shown in the S5 of Fig. 1, silicon wafer is impregnated in water-soluble comprising the organic acid containing carboxyl or acylate
The 5th process in liquid.In the 5th process S5, further effectively removes and do not completely remove in the 4th process and remain on wafer surface
Metal impurities and particle.These metal impurities and particle are the residues of the solid liquid interface of the 4th process, are forming wafer surface
Equilibrium state is in the moisture film of solvent molecule layer, it is unadsorbed in wafer surface.The metal impurities are formed by organic acid ion
Metallic complex salt.Adsorption organic acid ion in particle.As a result, becoming band by organic acid ion in the same manner as the 4th process
The metallic complex salt and particle of negative electrical charge are easy to be detached from from wafer surface.In the 5th process, it is possible to use with the 4th process be phase
With the solution comprising organic acid or acylate of composition, the concentration or type of organic acid or acylate can also mutually change.
For the type and concentration of organic acid or acylate in aqueous solution used in this process, according to being removed
Metal impurities type and determine.The concentration of organic acid or acylate is preferably 0.001 mass % or more, more preferably
0.003~10 mass %.Complexing by the metal impurities ion for 0.001 mass % or more, to dissociate from wafer surface
Become abundant.
It is suitble to the organic acid used or acylate same as ones listed in the 4th process in this process.
In aqueous solution used in this process, micro hydrofluoric acid is preferably further added.Thus, it is possible to slightly etch
Be formed in the natural oxide film of wafer surface, and by natural oxide film particle and metal impurities to be easily transferred into this water-soluble
In liquid.That is, while removing natural oxide film, the metal that can also be removed in natural oxide film is miscellaneous by addition hydrofluoric acid
Matter.At this point, the concentration of hydrofluoric acid is preferably 0.1 mass % hereinafter, more preferably 0.01 mass % or less.If more than 0.1 matter
% is measured, then the natural oxide film on surface is exceedingly etched, and thus the surface potential of the chip in aqueous solution changes, therefore
It is possible that causing adhering to again for particle and metal.
Dip time in this process is not particularly limited, preferably 3 minutes or more and 10 minutes or less.By being 3
Minute or more, above-mentioned required function and effect can be fully obtained, by imitating for 10 minutes hereinafter, washing will not be undermined
Rate.The temperature of aqueous solution is not particularly limited, such as can be for 15 DEG C or more and 30 DEG C hereinafter, typically can be room temperature
(25℃)。
(the 6th process)
Secondly, carrying out the 6th process being impregnated in silicon wafer in pure water as shown in the S6 of Fig. 1.In the 6th process S6, removal the
The residual component of organic acid used in 4 processes and the 5th process or acylate and the organic matter for being attached to wafer surface.
That is, the organic matter for being attached to wafer surface is before being oxidized in the 7th process later and being adhered to wafer surface, this
6 processes are removed.6th process be with the 1st above-mentioned process step combinations for efficiently reduce partial size be more than 0.045 μm and deficiency
The important procedure of the particle of 0.1 μm of intermediate sizes.
Dip time in this process is not particularly limited, preferably 3 minutes or more and 10 minutes or less.By being 3
Minute or more, above-mentioned required function and effect can be fully obtained, by imitating for 10 minutes hereinafter, washing will not be undermined
Rate.The temperature of pure water is not particularly limited, preferably 15 DEG C or more and 50 DEG C hereinafter, more preferably 18 DEG C or more and 25 DEG C with
Under.
(the 7th process)
Finally, be impregnated in silicon wafer comprising selected from dissolved ozone aqueous solution, nitric acid and peroxidating as shown in the S7 of Fig. 1
The 7th process in the 3rd one kind or two or more oxidation solution of aqueous solution of hydrogen.In the 7th process S7, first, improve pollution chip
The removal effect of surface and its neighbouring silicide metalloid (especially Cu)；Second, it is incomplete in the 6th process to decompose removal
Remove and be attached to the organic matter of wafer surface；Third chemically protects the wafer surface after washing with oxidation film.
Cu is directly dissolved in the high slightly acid solution of oxidizing potential and is removed.In addition, by by wafer surface chemical oxidation
Film is protected, and the attachment of the particle of solid gas interface is reliably prevented.In particular, dissolved ozone aqueous solution is rich at low concentrations
Oxidability and easy acquisition.Therefore, the 3rd oxidation solution is preferably dissolved ozone aqueous solution.
Ozone concentration in dissolved ozone aqueous solution is preferably 15ppm or more and 30ppm or less.In this process, it needs
Remaining organic acid is decomposed, it is therefore desirable to be the concentration higher than the ozone concentration in the 1st process and the 3rd process, preferably make smelly
Oxygen concentration is 15ppm or more.In addition, the dissolution of the ozone in pure water is limited to about 30ppm.
Dip time in this process is not particularly limited, preferably 3 minutes or more and 10 minutes or less.By being 3
Minute or more, above-mentioned required function and effect can be fully obtained, by imitating for 10 minutes hereinafter, washing will not be undermined
Rate.The temperature of 3rd oxidation solution is not particularly limited, such as can be for 15 DEG C or more and 30 DEG C hereinafter, typically can be
Room temperature (25 DEG C).
The washing methods of the silicon wafer of present embodiment from the description above can not only reduce 0.1 μm of partial size or more
Big particle, and can reduce by 0.045 μm of partial size small particle and partial size below is more than 0.045 μm and less than 0.1 μ
The particle of the intermediate sizes of m.
Embodiment
(example of the present invention)
Unwashed 25 silicon wafers until finished product is ground will be conventionally carried out, carried out under the following conditions
Carrying out washing treatment.Firstly, it is smelly that each chip to be impregnated in the dissolution that ozone concentration is 5ppm at 25 DEG C of liquid temperature as the 1st process
5 minutes in oxygen aqueous solution.Secondly, as the 2nd process, by each water immersion in 60 DEG C of liquid temperature of SC-1 solution (H2O2Concentration: 2.6
Quality %, NH4OH concentration: 0.6 mass %, surplus: the mixed liquor of pure water) in 5 minutes.The process is carried out by supersound washing.
Secondly, each chip is impregnated at 20 DEG C of liquid temperature 5 in the dissolved ozone aqueous solution that ozone concentration is 5ppm as the 3rd process
Minute.Secondly, preparing molten obtained by oxalic acid of the 0.06 mass % as organic acid to being mixed relative to pure water as the 4th process
Aqueous solution obtained by 0.05 mass % hydrofluoric acid is added in liquid, at 20 DEG C of liquid temperature, by each water immersion 5 minutes.Secondly, conduct
5th process prepares solution obtained by adding oxalic acid of the 0.6 mass % as organic acid relative to pure water, will at 20 DEG C of liquid temperature
Each water immersion 5 minutes.Secondly, as the 6th process, by each water immersion 5 minutes in 20 DEG C of liquid temperature of pure water.Finally, making
For the 7th process, each chip is impregnated at 20 DEG C of liquid temperature in the dissolved ozone aqueous solution that ozone concentration is 20ppm 5 minutes.
(comparative example 1)
The 1st process and the 6th process are not carried out, in addition to this, using method identical with example of the present invention, have washed 25 silicon wafers
Piece.The washing methods is equivalent to washing methods described in patent document 1.
(comparative example 2)
The 6th process is not only carried out, in addition to this, using method identical with example of the present invention, has washed 25 silicon wafers.The washing
Method is equivalent to the washing methods that the 1st process has only been added in the washing methods described in patent document 1.
(comparative example 3)
The 1st process is not only carried out, in addition to this, using method identical with example of the present invention, has washed 25 silicon wafers.The washing
Method is equivalent to the washing methods that the 6th process has only been added in the washing methods described in patent document 1.
The evaluation > of < particle number
It is right respectively using the surface of each chip after laser particle counter (KLA-tencor corporation, SP-2) measurement washing
0.1 μm of partial size or more of LPD, partial size are more than that 0.045 μm and the LPD less than 0.1 μm and 0.045 μm of partial size LPD below is carried out
It counts.The average value of 25 LPD numbers in example of the present invention and comparative example 1~3 is shown in Table 1.
[table 1]
As shown in Table 1, in example of the present invention, with comparative example 1~3 likewise it is possible to fully reduce by 0.1 μm of partial size or more big
Particle.In addition, can also fully reduce by 0.045 μm of partial size small particle and partial size below is more than in example of the present invention
The particle of 0.045 μm and the intermediate sizes less than 0.1 μm.In particular, the particle about intermediate sizes, although in patent document 1
The comparative example 2 of the 1st process has only been added in the washing methods or has only been added in the comparative example 3 of the 6th process, has less been obtained
Effect must be reduced, but in the example of the present invention for having added both the 1st process and the 6th process, reduces effect and increases tremendously.
Industrial availability
The washing methods of silicon wafer according to the present invention can not only reduce 0.1 μm of partial size or more of big particle, Er Qieke
To reduce the particle that 0.045 μm of partial size small particle and partial size below are more than 0.045 μm and the intermediate sizes less than 0.1 μm.
Description of symbols
The 1st process of S1
The 2nd process of S2
The 3rd process of S3
The 4th process of S4
The 5th process of S5
The 6th process of S6
The 7th process of S7.
Claims (6)
1. the washing methods of silicon wafer, which is characterized in that have following processes:
Silicon wafer is impregnated in comprising a kind or 2 selected from dissolved ozone aqueous solution, nitric acid and aqueous hydrogen peroxide solution by the 1st process
Kind or more the 1st oxidation solution in；
Aforementioned silicon wafer after aforementioned 1st process, is impregnated in the aqueous solution comprising hydrogen peroxide and ammonium hydroxide by the 2nd process
In；
After aforementioned 2nd process, aforementioned silicon wafer is impregnated in comprising selected from dissolved ozone aqueous solution, nitric acid and mistake for 3rd process
In the 2nd one kind or two or more oxidation solution for aoxidizing aqueous solution of hydrogen；
After aforementioned 3rd process, aforementioned silicon wafer is impregnated in comprising organic acid or acylate with carboxyl for 4th process
And in the aqueous solution of hydrofluoric acid；
After aforementioned 4th process, aforementioned silicon wafer is impregnated in comprising organic acid or acylate containing carboxyl for 5th process
Aqueous solution in；
After aforementioned 5th process, aforementioned silicon wafer is impregnated in pure water for 6th process；And
After aforementioned 6th process, aforementioned silicon wafer is impregnated in comprising selected from dissolved ozone aqueous solution, nitric acid and mistake for 7th process
In the 3rd one kind or two or more oxidation solution for aoxidizing aqueous solution of hydrogen.
2. the washing methods of silicon wafer described in claim 1, wherein aforementioned 1st oxidation solution, aforementioned 2nd oxidation solution and aforementioned
3rd oxidation solution is respectively the 1st~the 3rd dissolved ozone aqueous solution.
3. the washing methods of silicon wafer as claimed in claim 2, wherein the ozone in aforementioned 1st and the 2nd dissolved ozone aqueous solution
Concentration is 5ppm or more and 10ppm hereinafter, the ozone concentration in aforementioned 3rd dissolved ozone aqueous solution is 15ppm or more and 30ppm
Below.
4. the washing methods of described in any item silicon wafers of claims 1 to 3, wherein aforementioned used in aforementioned 4th process
The concentration of hydrofluoric acid in aqueous solution is 0.05 mass % or more and 1.0 mass % or less.
5. the washing methods of described in any item silicon wafers of Claims 1 to 4, wherein in aforementioned 4th process and the aforementioned 5th
The concentration of organic acid or acylate in aqueous solution used in process is 0.001 mass % or more.
6. the washing methods of described in any item silicon wafers of Claims 1 to 5, wherein aforementioned organic acid or acylate are
One kind or two or more organic acid or its salt selected from the following: oxalic acid, citric acid, succinic acid, ethylenediamine tetra-acetic acid, tartaric acid,
Salicylic acid, formic acid, maleic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, benzoic acid, acrylic acid, adipic acid, third
Diacid, malic acid, glycolic, phthalic acid, terephthalic acid (TPA) and fumaric acid.
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| CN113736580A (en) * | 2021-09-03 | 2021-12-03 | 上海中欣晶圆半导体科技有限公司 | Mixed acid cleaning solution for cleaning and polishing silicon wafer and cleaning method for polished silicon wafer |
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