CN107068540A - The cleaning method of chip - Google Patents
The cleaning method of chip Download PDFInfo
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- CN107068540A CN107068540A CN201611162059.6A CN201611162059A CN107068540A CN 107068540 A CN107068540 A CN 107068540A CN 201611162059 A CN201611162059 A CN 201611162059A CN 107068540 A CN107068540 A CN 107068540A
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- water repellency
- chip
- chemical solution
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- 238000000034 method Methods 0.000 title claims abstract description 120
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- 238000009835 boiling Methods 0.000 claims abstract description 79
- 230000008569 process Effects 0.000 claims abstract description 64
- 230000002940 repellent Effects 0.000 claims abstract description 31
- 239000005871 repellent Substances 0.000 claims abstract description 31
- 238000006073 displacement reaction Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000002352 surface water Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 228
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- 239000002585 base Substances 0.000 claims description 106
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- AHJCYBLQMDWLOC-UHFFFAOYSA-N n-methyl-n-silylmethanamine Chemical compound CN(C)[SiH3] AHJCYBLQMDWLOC-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 description 1
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- 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
- H01L21/02057—Cleaning during device manufacture
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/162—Organic compounds containing Si
-
- C11D2111/22—
Abstract
The present invention provides a kind of cleaning method of chip.[problem] is provided to be used to improve the cleaning method for easily inducing the matting that pattern topples in the manufacture method of the chip on surface with relief pattern.[solution] described cleaning method is the cleaning method for the chip that surface has relief pattern, and it at least has following process：The process for cleaning above-mentioned chip (1) with cleaning fluid (8)；The process that the cleaning fluid (8) for the recess (4) for being held in chip (1) after cleaning is replaced with water repellency chemical solution (9)；The process for drying chip (1), boiling point of the above-mentioned cleaning fluid (8) comprising more than 80 mass % is 55~200 DEG C of solvent, the temperature of the water repellency chemical solution (9) supplied in process by making above-mentioned displacement is 40 DEG C of boiling points less than the water repellency chemical solution (9), so as at least make above-mentioned recess surface water repellent.
Description
It is December 20, Application No. 2011800633494, entitled " chip in 2011 applying date that this division, which is,
Cleaning method " application divisional application.
Technical field
The present invention relates to the cleaning technique of substrate (chip) in semiconductor devices manufacture etc..
Background technology
In network, the semiconductor devices of digital household appliances, it is desirable to further high-performance/multifunction, low power consumption
Change.Therefore the miniaturization of circuit pattern is promoted, therewith together, causes the granularity that fabrication yield is reduced also just small
Change.As a result, use the matting for being used for removing the polluters such as the particle of microminiaturization more, as a result matting accounts for whole
3~4 one-tenth of semiconductor fabrication sequence.
On the other hand, in the cleaning of the mixing cleaning agent of the utilization ammonia carried out in the past, along with the fine of circuit pattern
Change, damage of its alkalescence to chip turns into problem.Therefore, carrying out to the less such as diluted hydrofluoric acid system cleaning agent of damage
Substitute.
Thus, caused by cleaning to the damage of chip the problem of improved, but accompany with the miniaturization of semiconductor devices
Pattern depth-width ratio rise caused by the problem of significantly change.That is, after cleaning or rinse, pattern is caused when gas-liquid interface is by pattern
The phenomenon toppled over, yield rate be greatly reduced as it is serious the problem of.
In patent document 1, as the gimmick that pattern topples over is suppressed, following technologies are disclosed：Pass through pattern in gas-liquid interface
Before, cleaning fluid is replaced as 2- propyl alcohol by water.But, it is stated that it is capable of the depth-width ratio of corresponding pattern and such as the following there is boundary for 5.
In addition, in patent document 2, as the gimmick that pattern topples over is suppressed, disclose using corrosion-resisting pattern as object skill
Art.The gimmick is by making capillary force be reduced to the limit so as to suppress the gimmick that pattern topples over.But, the technology of the disclosure will be anti-
Corrosion figure case is modified as object to resist itself, and then finally can together be removed with resist, therefore need not be examined
Consider the minimizing technology of dried inorganic agent, it is impossible to suitable for this purpose.
In addition, being used as the gimmick for preventing that the pattern of semiconductor devices from toppling over, it is proposed that the utilization of critical fluids and liquid nitrogen
Utilize.Patent document 3 discloses that a kind of method, it is characterised in that methods described will solidify residual after photoresist, etching
Slag and/or bottom anti reflective coatings (BARC) have residue and/or bottom after same solidification photoresist, etching from the upper side
The microelectronic element of portion's anti-reflection coating (BARC) is removed, and methods described includes following process：To above-mentioned solidification is photic anti-
Lose residue and/or BARC after agent, etching has the microelectronic element of above-mentioned photoresist, residue and/or BARC from the upper side
Microelectronic element is contacted with dense fluid condensation thing under sufficient time and sufficient contact conditions at least partly removing；
Above-mentioned dense fluid condensation thing includes at least one kind of secondary solvent, optional at least one kind of oxidant/free radical supply source, optional
At least one kind of surfactant and optional at least one kind of silicon-containing layer inertia agent, above-mentioned concentrate comprising following compositions (I) or
(II) it is at least one kind of in：
(I) at least one kind of fluoride providing source and optional at least one kind of acid and
(II) at least one kind of acid.
But, special cleaning device is needed compared with conventional cleaning, in addition, production capacity difference etc. is difficult to be applicable
In mass-production process.
A kind of cleaning method is disclosed in patent document 4,5, it is formed with by oxidation etc. to utilizing comprising the film of silicon
The wafer surface of concaveconvex shape pattern carries out surface modification, and using water soluble surfactant active or silane coupler on the surface
Water repellency overlay film is formed, capillary force is reduced, prevents collapsing for pattern.
A kind of surface treatment method is disclosed in patent document 6,7, it includes following process：Using containing silylated
What the surface treatment liquid of agent and solvent was formed to the resin pattern that is arranged on substrate or by being etched on substrate is eclipsed needle drawing
The process that the surface of case is handled；Resin pattern after to being handled using surface treatment liquid is etched what pattern was cleaned
Process.
Patent Document 8 discloses a kind of cleaning method of semiconductor devices, it includes following process：Being formed has substrate
With the process of the semiconductor devices of the dielectric layer of the structure protruded from the substrate；Above-mentioned semiconductor device is cleaned with aqueous solution
The process of structure；Above-mentioned aqueous solution is replaced as to the process of the 1st liquid after above-mentioned cleaning；After above-mentioned displacement with comprising with it is upper
The 2nd liquid for stating the side wall reaction of prominent structure and the hydrophobicity inorganic agent in sidewall surfaces formation hydrophobic layer handles above-mentioned knot
The process of structure.
Patent Document 9 discloses a kind of cleaning method of silicon wafer surface, the cleaning agent of following silicon wafers is it used,
The cleaning agent is the silicon wafer cleaning agent that surface has fine relief pattern, and the cleaning agent includes cleaning fluid A, cleaning fluid
B, above-mentioned cleaning fluid A is formed by aqueous solution, and cleaning fluid B is by the recess water repellent of relief pattern, and above-mentioned cleaning fluid B is by alcoholic solution
And water or acidic aqueous solution are mixed, above-mentioned alcoholic solution includes water repellency compound and alcoholic solvent, above-mentioned water repellency chemical combination
The water-disintegrable position for the unit that thing can be chemically bonded comprising generation with the element silicon of silicon wafer, hydrophobic group, by should
Refusing of mixing is made in water repellency compound in the way of being 0.2~20 mass % in the mass % of total amount 100 in cleaning fluid B
Aqueous rinsing liquid, so that assuming the capillary force when the recess of the silicon wafer surface by cleaning fluid B water repellents maintains water
For 2.1MN/m2Below.
Patent Document 10 discloses a kind of cleaning method of silicon wafer surface, following silicon wafer cleanings are it used
Agent, the cleaning agent is the silicon wafer cleaning agent that surface has fine relief pattern, and the silicon wafer is at least wrapped with cleaning agent
Cleaning fluid containing water system and for the water repellency cleaning fluid at least recess water repellent for making relief pattern in cleaning process, by making
The water repellency cleaning fluid is by refusing comprising the reactive moieties and hydrophobic group that can be chemically bonded with the element silicon of silicon wafer
Aqueous compounds are formed, or total amount 100 mass % of the mixing comprising relative to the water repellency cleaning fluid is more than 0.1 mass %
The water repellency compound and organic solvent so that assume in the silicon wafer surface by the water repellency cleaning fluid water repellent
Capillary force when recess maintains water is 2.1MN/m2Below.
A kind of cleaning method of silicon wafer surface is disclosed in patent document 11, following silicon wafer cleanings are it used
Agent, the cleaning agent is the silicon wafer cleaning agent that surface has fine relief pattern, and the silicon wafer is at least wrapped with cleaning agent
Cleaning fluid containing water system and for the water repellency cleaning fluid at least recess water repellent for making relief pattern in cleaning process, the water repellent
Property cleaning fluid mixing contain water repellency compound and organic solvent, above-mentioned water repellency compound is comprising can be with the silicon of silicon wafer member
The reactive moieties and hydrophobic group of element chemical bonding, above-mentioned organic solvent include the solvent of Nitrogen element, the water repellency
Compound is mixed in the way of 0.1~50 mass % by the mass % of total amount 100 relative to the water repellency cleaning fluid and included, and then,
The element that the solvent of the Nitrogen element is made into being bonded with nitrogen is carbon, so that assuming passing through the water repellency cleaning fluid water repellent
Capillary force when maintaining water of the recess of silicon wafer surface be 2.1MN/m2Below.
A kind of cleaning method of silicon wafer surface is disclosed in patent document 12, following silicon wafer cleanings are it used
Agent, the cleaning agent is characterised by that it is the silicon wafer cleaning agent that surface has fine relief pattern, and the silicon wafer is used
Cleaning agent comprises at least water system cleaning fluid and for the water repellency at least recess water repellent for making relief pattern in cleaning process
Cleaning fluid, water repellency cleaning fluid mixing contains water repellency compound and organic solvent, and above-mentioned water repellency compound is included can
The reactive moieties and hydrophobic group being chemically bonded with the element silicon of silicon wafer, above-mentioned organic solvent comprise at least alcoholic solvent.
In addition, as above-mentioned chip, there is the chip of element silicon usually using surface, along with the variation of pattern, open
Begin that there is the chip of the element of titanium, tungsten, aluminium, copper, tin, tantalum and ruthenium etc using surface.Disclosed in patent document 13 in following
Hold, during the cleaning for the chip that fine relief pattern is formed with surface, at least recess table of the relief pattern in the chip
The part in face includes at least one kind of thing in the group being made up of titanium, titanium nitride, tungsten, aluminium, copper, tin, tantalum nitride, ruthenium and silicon
Matter, by using the change for including the water repellency diaphragm forming agent for forming water repellency diaphragm at least the above recess surface
Solution is learned, can improve and the matting that pattern topples over easily is induced in above-mentioned chip.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-198958 publications
Patent document 2：Japanese Unexamined Patent Publication 5-299336 publications
Patent document 3：Japanese Unexamined Patent Application Publication 2008-547050 publications
Patent document 4：No. 4403202 publications of Japanese Patent No.
Patent document 5：Japanese Unexamined Patent Publication 2010-114467 publications
Patent document 6：Japanese Unexamined Patent Publication 2010-129932 publications
Patent document 7：No. 2010/047196 pamphlet of International Publication No.
Patent document 8：No. 2010/0122711 publication of U.S. Patent Publication
Patent document 9：No. 2010/074134 pamphlet of International Publication No.
Patent document 10：Japanese Unexamined Patent Publication 2010-192878 publications
Patent document 11：Japanese Unexamined Patent Publication 2010-192879 publications
Patent document 12：Japanese Unexamined Patent Publication 2010-272852 publications
Patent document 13：Japanese Patent No. 4743340
The content of the invention
Problems to be solved by the invention
The present invention relates to the cleaning technique of substrate (chip), in semiconductor devices manufacture etc., the cleaning technique is to improve
For the purpose of the fabrication yield for the device that especially fine and high depth-width ratio circuit pattern is crossed；In particular, the present invention relates to refuse
Aqueous chemical solution etc., the water repellency chemical solution etc. easily induces the bump maps that surface has the chip of relief pattern to improve
For the purpose of the matting that case is toppled over.Recorded in patent document 4,5 makes liquid temperature rise so as to promote by carrying out annealing
The reaction of surface conditioning agent, but do not account for making completely surface conditioning agent it is rapid over to handled object surface (displacement), i.e.
Just surface is also promoted with the degree that can be sufficiently formed water repellency overlay film in the state of replacing in the displacement way not being fully completed
There is room for improvement in the reaction of inorganic agent, the shortening of the time required for surface treatment.In addition, on patent document 6~13,
Also because it is same the reasons why, there is room for improvement in the shortening of time required for surface treatment.The problem of the present invention is to carry
For a kind of cleaning method of chip, the cleaning method makes holding by least recess surface formation water repellency overlay film in chip
Reduced in the liquid of the recess with the interaction of the recess surface, so that toppling over for relief pattern is successfully prevented, the cleaning
Method does not damage production capacity, can be economical and more efficiently cleans chip.
The solution used to solve the problem
The cleaning method of the chip of the present invention is characterised by that it is the cleaning side for the chip that surface has relief pattern
Method, it at least has following process：
The process that above-mentioned chip is cleaned with cleaning fluid；
The process that the cleaning fluid for the recess for being held in chip after cleaning is replaced with water repellency chemical solution；
The process for drying chip,
Boiling point of the above-mentioned cleaning fluid comprising more than 80 mass % is 55~200 DEG C of solvent,
The temperature of the water repellency chemical solution supplied in process by making above-mentioned displacement is 40 DEG C and refused less than this
The boiling point of aqueous chemical solution, so as at least make above-mentioned recess surface water repellent.It should be noted that this specification mid-boiling point is
Refer to the value of the state of 1 atmospheric pressure.In addition, the boiling point of water repellency chemical solution refers to contained by the water repellency chemical solution
The boiling point of most compositions is measured in composition by quality ratio.
Pattern is produced when toppling in the drying after cleaning chip with cleaning fluid gas-liquid interface by pattern.It is said that its reason
It is, between the big part of the depth-width ratio of pattern and small part, produces the raffinate difference in height of cleaning fluid, thus act on figure
The capillary force of case produces difference.
Therefore, if reducing capillary force, the difference reduction of the capillary force caused by raffinate difference in height can expect that pattern topples over
Eliminate.The size of capillary force is the P obtained with formula as shown below absolute value, according to the formula, if reducing γ or cos θ,
Expectation can reduce capillary force.
P=2 × γ × cos θ/S
(in formula, γ is the surface tension for the liquid for being held in recess, and θ is recess surface and the liquid institute for being held in recess
Into contact angle, S be recess width.)
Above-mentioned water repellency chemical solution forms water repellency overlay film by least recess surface in above-mentioned relief pattern, so that
Making the surface energy of the part reduces, and (interface) makes interaction, such as hydrogen between water, other liquid and the part surface
Key, intermolecular force etc. are reduced.Particularly for water, the effect for reducing interaction is big, but to water and water beyond
Liquid beyond the mixed liquor of liquid, water also has the effect of reduction interaction.Thereby, it is possible to increase liquid to article surface
Contact angle.
Cleaning fluid is replaced as water repellency chemical solution as described above, at least recess of relief pattern maintains the chemical solution
During liquid, above-mentioned water repellency overlay film is formed with least recess surface of the relief pattern.Therefore, gone in liquid from recess
Except when, by dry when, be formed with above-mentioned water repellency overlay film at least recess surface of above-mentioned relief pattern, therefore act on this
The capillary force of recess diminishes, it is difficult to occurs pattern and topples over.
In addition, in order that at least recess surface formation with above-mentioned water repellency chemical solution with the short time in relief pattern is refused
Aqueous overlay film, the overlay film Forming ability and rapid replaced with water repellency chemical solution for improving the chemical solution is held in the clear of recess
Washing lotion is effective.
If the temperature of the water repellency chemical solution supplied in the process for making above-mentioned displacement is more than 40 DEG C, promote the water repellent
Property chemical solution reaction and absorption, overlay film Forming ability improve, above-mentioned water repellency overlay film as a result can be formed with the short time.Separately
Outside, even if can also be sufficiently formed water repellency overlay film in the state of in the displacement way that displacement is not fully completed.But, if making
The temperature for stating water repellency chemical solution is the boiling point of the chemical solution, then the chemical solution easily evaporates rapidly, therefore chip table
Face is easily dried, thus not preferred.Therefore, above-mentioned water repellency chemical solution with 40 DEG C less than the water repellency chemical solution
Boiling point, be preferably 50 DEG C less than (- 10 DEG C of the boiling point of above-mentioned water repellency chemical solution), more preferably 70 DEG C with
Upper and less than (- 10 DEG C of the boiling point of above-mentioned water repellency chemical solution) temperature is supplied to wafer surface.
If in addition, boiling point of the above-mentioned cleaning fluid comprising more than 80 mass % is 55~200 DEG C of solvent, in supplying temperature
During for more than 40 DEG C of water repellency chemical solution, the cleaning fluid is easily evaporated, therefore the cleaning fluid of recess is easily put with the short time
Change water repellency chemical solution into.As a result, forming water repellency overlay film with the short time.In addition, by making the above-mentioned chemistry supplied
The temperature of solution is 40 DEG C of temperature less than the boiling point of the chemical solution, in the upper of the recess with being held in relief pattern
Easily generation diffusion, convection current between cleaning fluid is stated, as a result, above-mentioned cleaning fluid can be replaced as into water repellency chemistry with the short time
Solution.Therefore, the above-mentioned cleaning fluid particularly preferably boiling point comprising more than 80 mass % is 60~180 DEG C of solvent, further excellent
Boiling point of the choosing comprising more than 80 mass % is 70~160 DEG C of solvent.If it should be noted that making above-mentioned cleaning fluid include 80 matter
The boiling point for measuring more than % is less than 55 DEG C of solvent, then in the process of cleaning fluid is replaced with water repellency chemical solution, supplies 40 DEG C
Less than the temperature of the boiling point of the water repellency chemical solution chemical solution when, there is a situation where the cleaning fluid bumping and should
The too fast situation of the evaporation rate of cleaning fluid, as a result, being possible to damage caused by the generation of bubble and bumping and to relief pattern
Wound.If in addition, making solvent of the boiling point more than 200 DEG C that above-mentioned cleaning fluid includes more than 80 mass %, chemical with water repellency
In the process of solution replacement cleaning fluid, the chemical solution of the temperature of 40 DEG C of boiling points less than the water repellency chemical solution is supplied
During liquid, the evaporation of the cleaning fluid is slow, therefore needs prolonged tendency with above-mentioned displacement, as a result, in the presence of in order that brilliant
Piece surface exhibits, which go out water repellency, needs prolonged tendency.If it should be noted that making above-mentioned cleaning fluid be 55~200 DEG C of boiling point
Solvent, then the temperature of above-mentioned water repellency chemical solution is easily managed to avoid the evaporation drastically of cleaning fluid, the generation of bubble
And bumping, thus more preferably.
Above-mentioned cleaning fluid is preferably selected from being mixed with organic solvent, acid, alkali, oxidant by organic solvent, water, in water
At least one kind of aqueous solution composition group at least one kind of liquid.It should be noted that being mixed sometimes below by water, in water
At least one kind of aqueous solution closed in organic solvent, acid, alkali, oxidant is designated as water system liquid.
On above-mentioned water repellency chemical solution, cleaning fluid is replaced in the matting of chip of relief pattern is formed with
Used into the chemical solution.In addition, the water repellency chemical solution after above-mentioned displacement can also be replaced as other cleaning fluids.
Above-mentioned water repellency overlay film may not be continuously formed, moreover, may not be formed uniformly, it is more excellent in order to assign
Water repellency, it is more preferably continuous and be formed uniformly.
Above-mentioned chip is (to be designated as " silicon systems sometimes below in chip of the surface of the recess of relief pattern comprising element silicon
Chip "), above-mentioned water repellency chemical solution preferably comprises the silicon compound A of following formulas [1] expression, or preferably comprises silication
Compound A and acid or alkali.In addition, this will be designated as with the method for water repellency chemical solution cleans silicon systems chip using the silicon systems chip
The 1st mode (being designated as sometimes below " the 1st method ") of invention.It should be noted that above-mentioned chemical solution is designated as into " silicon sometimes
It is chip water repellency chemical solution ".
(R1)aSi(H)bX1 4-a-b [1]
[in formula [1], R1It is each independently of the others, is the carbon optionally replaced comprising part or all of protium by fluorine element
Atomicity is 1 valency organic group of 1~18 1 valency alkyl.In addition, X1Be each independently of the others, represent be selected from by with element silicon key
The element that the element of conjunction is 1 valency functional group of nitrogen, be bonded with element silicon is 1 valency functional group, halogen radical, itrile group and the-CO- of oxygen
NH-Si(CH3)3At least one kind of group in the group of composition.A is 1~3 integer, and b is 0~2 integer, a and b add up to 1~
3。]
In addition, above-mentioned water repellency chemical solution includes acid, the acid is preferably selected from by hydrogen chloride, sulfuric acid, perchloric acid, phosphorus
Carboxylic acid and its acid anhydrides, boron alkyl acid esters, virtue that the sulfonic acid and its acid anhydrides, following formulas [3] of sour, following formulas [2] expressions are represented
The silication that ylboronic acid ester, three (trifluoroacetyl epoxide) boron, tri-alkoxy boroxin, boron trifluoride, following formulas [4] are represented is closed
It is at least one kind of in the group of thing B compositions.
R2S(O)2OH [2]
[in formula [2], R2It is 1 valency that part or all of protium is optionally 1~18 by the carbon number that fluorine element replaces
Alkyl.]
R3COOH [3]
[in formula [3], R3It is 1 valency that part or all of protium is optionally 1~18 by the carbon number that fluorine element replaces
Alkyl.]
(R4)cSi(H)dX2 4-c-d [4]
[in formula [4], R4It is each independently of the others, is the carbon atom that part or all of protium is optionally replaced by fluorine element
Number is 1~18 1 valency alkyl.In addition, X2It is each independently of the others, represents to be selected from by chloro ,-OCO-R5(R5It is part or all
The 1 valency alkyl that protium is optionally 1~18 by the carbon number that fluorine element replaces) and-OS (O)2-R6(R6It is part or all
The carbon number that protium is optionally replaced by fluorine element is 1~18 1 valency alkyl) at least one kind of group in the group of composition.C is 1
~3 integer, d is 0~2 integer, and c and d's adds up to 1~3.]
In addition, above-mentioned acid is preferably the silicon compound B that above-mentioned formula [4] represents, it is preferably selected from by trimethyl silyl
Base trifluoro-acetate, trimethylsilyl triflate, dimetylsilyl trifluoro-acetate, dimethyl silane
Base triflate, Butyldimethylsilyl trifluoro-acetate, Butyldimethylsilyl triflate, oneself
Base dimetylsilyl trifluoro-acetate, hexyl dimetylsilyl triflate, octyldimethyl silicyl
Trifluoro-acetate, octyldimethyl silicyl triflate, decyl dimethyl silicyl trifluoro-acetate, decyl two
Methyl silicane base triflate, dodecyl dimethyl silicyl trifluoro-acetate, dodecyl dimethyl first silicon
It is at least one kind of in the group of alkyl triflate composition.
In addition, above-mentioned water repellency chemical solution includes alkali, the alkali is preferably selected from by ammonia, N, N, N ', N '-tetramethyl second two
Amine, triethylenediamine, dimethylaniline, alkylamine, dialkylamine, trialkylamine, pyridine, piperazine, N- alkyl morpholines, following formulas
[5] it is at least one kind of in the group of the silicon compound C compositions represented.
(R7)eSi(H)fX3 4-e-f [5]
[in formula [5], R7It is each independently of the others, is the carbon atom that part or all of protium is optionally replaced by fluorine element
Number is 1~18 1 valency alkyl.In addition, X3It is each independently of the others, is the element being bonded with element silicon for nitrogen and fluorine member can be included
Element, the functional group of 1 valency of element silicon.E is 1~3 integer, and f is 0~2 integer, and e and f's adds up to 1~3.]
The water repellency overlay film formed using above-mentioned silicon systems chip with water repellency chemical solution is formed by following manner：It is above-mentioned
The X of formula [1]1Reacted with the silanol group of the reaction site as silicon systems wafer surface, silicon compound A and silicon systems chip silicon
Element chemistry is bonded.The R of above-mentioned formula [1]1Making the surface energy of above-mentioned recess reduces, in water, other liquid and the water repellency
(interface) makes interaction, reduced such as hydrogen bond, intermolecular force between overlay film surface, can increase liquid to article table
The contact angle in face.
Above-mentioned acid or alkali included in chemical solution successfully promote above-mentioned silicon compound A and the element silicon of silicon systems chip
Reaction.If above-mentioned silicon systems chip can be formed water repellency with the short time and be covered with there is the acid or alkali in water repellency chemical solution
Film.It should be noted that silicon systems wafer surface formation water repellency overlay film speed, show water repellent in silicon systems wafer surface
The speed of property is determined with speed that the reaction site of silicon systems wafer surface is combined by the composition from above-mentioned silicon compound A.If
There is above-mentioned acid or alkali, then the composition from above-mentioned silicon compound A can be with the relief pattern surface as silicon systems chip
The silanol group of reaction site reacts rapidly, therefore can assign water repellent to silicon systems wafer surface with the short time in surface treatment
Property.It should be noted that above-mentioned acid or alkali can also form a part for water repellency overlay film.
In addition, above-mentioned silicon compound A be preferably selected from by HMDS, trimethyl silyl dimethyl amine,
Trimethyl silyl diethylamide, tetramethyl-disilazane, dimetylsilyl dimethyl amine, dimetylsilyl two
Ethylamine, 1,3- dibutyl tetramethyl-disilazane, Butyldimethylsilyl dimethyl amine, Butyldimethylsilyl
Diethylamide, 1,3- dihexyls tetramethyl-disilazane, hexyl dimetylsilyl dimethyl amine, hexyl dimethyl silane
Base diethylamide, 1,3- dioctyls tetramethyl-disilazane, octyldimethyl silicyl dimethyl amine, octyldimethyl first silicon
Alkyl diethyl amine, 1,3- didecyls tetramethyl-disilazane, decyl dimethyl silicyl dimethyl amine, decyl dimethyl first
Silylation diethylamide, 1,3- bis- (dodecyl) tetramethyl-disilazane, dodecyl dimethyl silicyl dimethyl amine,
It is at least one kind of in the group of dodecyl dimethyl silicyl diethylamide composition.
In addition, above-mentioned chip is to be included on the surface of the recess of relief pattern in titanium, tungsten, aluminium, copper, tin, tantalum and ruthenium extremely
The chip (being designated as sometimes below " metal system chip ") of few a kind of element (being designated as sometimes below " metal series elements "), it is above-mentioned
Water repellency chemical solution preferably comprises what is constituted selected from the compound and its salt compound represented by following formula [6]~[12]
At least one kind of and solvent in group.It should be noted that above-mentioned chemical solution is designated as into " metal system chip water repellency sometimes
Learn solution ".In addition, the present invention will be designated as with the method for water repellency chemical solution cleans metal system chip using the metal system chip
The 2nd mode (being designated as sometimes below " the 2nd method ").
R8- P (=O)-(OH)g(R9)2-g [6]
[in formula [6], R8It is 1 valency that part or all of protium is optionally 1~18 by the carbon number that fluorine element replaces
Alkyl.R9It is each independently of the others, is that the carbon number optionally replaced comprising part or all of protium by fluorine element is 1~18
Alkyl 1 valency organic group.G is 0~2 integer.]
R10- C (=O)-X4 [7]
[in formula [7], R10Be comprising carbon number be 1~18 alkyl 1 valency organic group or be 1 comprising carbon number
1 valency organic group of~8 fluoroalkyl chain.X4Represent the group in the group being made up of fluorine-based, chloro, bromo and iodo.]
R11R12R13N [8]
[in formula [8], R11Be comprising carbon number be 1~18 alkyl 1 valency organic group or be 1 comprising carbon number
1 valency organic group of~8 fluoroalkyl chain.R12It is protium, comprising 1 valency organic group of the carbon number for 1~18 alkyl
Or include 1 valency organic group of the carbon number for 1~8 fluoroalkyl chain.R13It is protium, is 1~18 comprising carbon number
1 valency organic group of alkyl includes 1 valency organic group of the carbon number for 1~8 fluoroalkyl chain.]
R14- C (=O)-X5-X6 [9]
[in formula [9], R14Be comprising carbon number be 1~18 alkyl 1 valency organic group or be 1 comprising carbon number
1 valency organic group of~8 fluoroalkyl chain.X5Represent oxygen element or element sulphur, X6Represent to be selected from by protium, alkyl, aromatic series
Group, pyridine radicals, quinolyl, succinimido, dimaleoyl imino, benzoxazolyl, benzothiazolyl and BTA
Protium in group in the group of base composition, these groups is optionally replaced by organic group.]
R15(X7)h [10]
[in formula [10], X7Be each independently of the others, for select free isocyanate group, sulfydryl, aldehyde radical ,-CONHOH bases and comprising
At least one kind of group in the group of the ring structure composition of nitrogen, h is 1~6 integer, R15Be comprising carbon number be 1~18
The organic group of alkyl or the organic group for including the fluoroalkyl chain that carbon number is 1~8, the compound are with above-mentioned h
Select at least one kind of base in the group of free isocyanate group, sulfydryl, aldehyde radical ,-CONHOH bases and the ring structure composition comprising nitrogen
The compound of the protium of the identical quantity of group's substitution.]
R16-X8 [11]
[in formula [11], X8For the ring structure comprising element sulphur, R16It is protium, comprising the alkyl that carbon number is 1~18
1 valency organic group or include carbon number for 1~8 fluoroalkyl chain 1 valency organic group.]
R17- C (=O)-X9- C (=O)-R18 [12]
[in formula [12], R17Be comprising carbon number be 1~18 alkyl 1 valency organic group or be 1 comprising carbon number
1 valency organic group of~8 fluoroalkyl chain.R18It is for 1 valency organic group of 1~18 alkyl or comprising carbon comprising carbon number
Atomicity is 1 valency organic group of 1~8 fluoroalkyl chain.X9Represent oxygen element or element sulphur.]
On the water repellency overlay film formed using above-mentioned metal system chip with water repellency chemical solution, by using selected from upper
The compound of formula [6]~[12] expression and its compound of salt compound are stated, can be in above-mentioned metal system chip at least
Recess surface is formed.It should be noted that the formation of water repellency overlay film is completed as follows：Have to the material comprising metal series elements
The functional unit of compatibility is adsorbed onto the material surface for including metal series elements, and/or the functional unit and the material surface it is anti-
Answer and form chemical bond to adsorb.On above-mentioned functions unit, in formula [6] middle finger P-OH bases and/or the base of P=O basis representations
Group, in formula [7] middle finger-C (=O)-X4The group of expression, in formula [8] middle finger N element, formula [9] middle finger-C (=O)-
X5-X6The group of expression, in formula [10] middle finger (X7)hThe group of expression, in formula [11] middle finger-X8The group of expression, logical
Formula [12] middle finger-C (=O)-X9The group of-C (=O)-expression.Herein, refer to that Van der Waals force or electrostatic are mutual with compatibility
Effect etc. is acted between the above-mentioned material surface comprising metal series elements and the functional unit of above-claimed cpd.In addition, above-mentioned
The R of formula [6]8, formula [7] R10, formula [8] R11, formula [9] R14, formula [10] R15, formula [11] R16With
The R of formula [12]17With R18For the hydrophobic portion of above-claimed cpd, the compound is adsorbed in the above-mentioned metal system member of metal system chip
When plain, the hydrophobic portion is arranged laterally from the metal system wafer surface, as a result with following effects：Enable the surface of above-mentioned recess
Amount reduction, (interface) makes interaction, such as hydrogen bond, intermolecular work between water, other liquid and the water repellency overlay film surface
Firmly wait reduction.Thereby, it is possible to increase contact angle of the liquid to article surface.
In addition, the present invention is the water repellency chemical solution used in the cleaning method of the chip described in any of the above-described.
It should be noted that in this specification, in the case where referring to both silicon systems chip and metal system chip, only remembering sometimes
For " chip ".In addition, referring to silicon systems chip both water repellency chemical solution and metal system chip water repellency chemical solution
In the case of, only it is designated as sometimes " water repellency chemical solution ".
The effect of invention
The cleaning method of the present invention in the recess surface formation water repellency overlay film of chip, make to be held in the liquid of the recess with
The interaction reduction of the recess surface, the water repellency toppled over of relief pattern is successfully prevented thus, it is possible to be formed with the short time
Overlay film.Therefore, the surface carried out using the water repellency chemical solution of the present invention has the manufacture method of the chip of relief pattern
Productivity ratio is high.
Brief description of the drawings
Fig. 1 is to show that the schematic plan view of one of the chip 1 in the face with relief pattern 2 is made in surface.
Fig. 2 shows a part for the a-a ' sections in Fig. 1.
Fig. 3 shows that matting center dant 4 maintains the schematic diagram of the state of cleaning fluid 8.
Fig. 4 shows that water repellency chemical solution 9 is supplied to the shape that matting center dant 4 maintains the chip of cleaning fluid 8
The schematic diagram of state.
Fig. 5 shows that replacing process center dant 4 keeps water repellency chemical solution 9 and form the state of water repellency overlay film 12
Schematic diagram.
Embodiment
There is the cleaning method of the chip of relief pattern the present invention relates to a kind of surface, it is characterised in that it at least has
Following process：
The process that above-mentioned chip is cleaned with cleaning fluid；
The process that the cleaning fluid for the recess for being held in chip after cleaning is replaced with water repellency chemical solution；
The process for drying chip,
Boiling point of the above-mentioned cleaning fluid comprising more than 80 mass % is 55~200 DEG C of solvent,
The temperature of the water repellency chemical solution supplied in process by making above-mentioned displacement is 40 DEG C and refused less than this
The boiling point of aqueous chemical solution, so as at least make above-mentioned recess surface water repellent.
For there is the chip of relief pattern for above-mentioned surface, if removing liquid with various liquid rinses and by dry etc.
Body, then the width of recess is small, convex portion depth-width ratio is big, easily occurs pattern and topples over.The relief pattern such as Fig. 1 and Fig. 2 record that
Sample is defined.Fig. 1 shows that the schematic plan view of one of the chip 1 in the face with relief pattern 2 is made in surface, and Fig. 2 is shown in Fig. 1
A-a ' sections a part.As shown in Fig. 2 time interval of the width 5 of recess with convex portion 3 and convex portion 3, the depth-width ratio of convex portion
Represented with the value obtained by the height 6 of convex portion divided by the width 7 of convex portion.The width that pattern in matting topples in recess is
Below 70nm, particularly below 45nm, depth-width ratio easily occur when being more than 4, particularly more than 6.
In the cleaning method of the present invention, the boiling point comprising more than 80 mass % is kept to be 55 at least recess of relief pattern
The cleaning fluid of~200 DEG C of solvent, is put the cleaning fluid with the state that at least recess in relief pattern maintains the cleaning fluid
Change above-mentioned water repellency chemical solution into.
Fig. 3 shows that matting center dant 4 maintains the schematic diagram of the state of cleaning fluid 8.The chip of Fig. 3 schematic diagram shows
Go out a part for Fig. 1 a-a ' sections.Water repellency chemical solution is supplied to matting center dant 4 and maintains cleaning fluid 8
The chip of state.
Fig. 4 show water repellency chemical solution 9 be supplied to recess 4 maintain cleaning fluid 8 state chip state
Schematic diagram.Now, water repellency chemical solution 9 can be replaced as by cleaning fluid 8 in recess, but cleaning fluid 8 includes 80 mass %
Boiling point above is 55~200 DEG C of solvent, and then water repellency chemical solution 9 is heated to 40 DEG C less than the water repellency
The boiling point of chemical solution, thus for example, by such diffusion, convection current, cleaning fluid and water repellency chemical solution shown in 10 in figure
Mixing easily carry out, in addition, the evaporation of cleaning fluid as shown in 11 in figure is easily carried out, as a result above-mentioned displacement is with short
Time is carried out.
Fig. 5 shows that replacing process center dant 4 keeps water repellency chemical solution 9 and form the state of water repellency overlay film 12
Schematic diagram.By forming water repellency overlay film 12 on the surface of recess 4, so that the surface is by water repellent.
Hereinafter, the 1st method is illustrated.Above-mentioned silicon systems chip preferably comprises above-mentioned formula [1] expression with water repellency chemical solution
Silicon compound A or include silicon compound A and acid or alkali.
It is used as the X of above-mentioned formula [1]1The element being bonded with element silicon of one not only can be with for 1 valency functional group of nitrogen
Comprising hydrogen, carbon, nitrogen, oxygen, the elements such as silicon, sulphur, halogen can also be included.As the example of the functional group, there are NCO, ammonia
Base, dialkyl amido, isothiocyanate group, azido, acetamido ,-N (CH3)C(O)CH3、-N(CH3)C(O)CF3,-N=C
(CH3)OSi(CH3)3,-N=C (CF3)OSi(CH3)3、-NHC(O)-OSi(CH3)3、-NHC(O)-NH-Si(CH3)3, imidazole ring
(following formula [13]), oxazolidones ring (following formula [15]), morpholine ring (following formula [14]) ,-NH-C (O)-Si (CH3)3、-N(H)2-i(Si
(H)jR19 3-j)i(R19It is part or all of protium optionally by the 1 valency alkyl that the carbon number that fluorine element replaces is 1~18, i
For 1 or integer that 2, j are 0~2) etc..
[chemical formula 1]
In addition, being used as the X of above-mentioned formula [1]1The element being bonded with element silicon of one for oxygen 1 valency functional group not only
Hydrogen, carbon, nitrogen, oxygen can be included, the elements such as silicon, sulphur, halogen can also be included.As the example of the organic group, there is alcoxyl
Base ,-OC (CH3)=CHCOCH3、-OC(CH3)=N-Si (CH3)3、-OC(CF3)=N-Si (CH3)3、-O-CO-R20(R20For one
Part or all of protium is optionally by 1 valency alkyl that the substituted carbon number such as fluorine element is 1~18), part or all of hydrogen
Element is optionally by substituted alkyl sulfonic acid ester group such as fluorine element etc..
In addition, being used as the X of above-mentioned formula [1]1The halogen radical of one have chloro, bromo, iodo etc..
In addition, the R of above-mentioned formula [1]1Be make above-mentioned water repellency overlay film surface energy reduce and water, other liquid with
(interface) reduction interaction, the hydrophobic portion such as hydrogen bond, intermolecular force between the water repellency overlay film surface.Particularly
For water, the effect for reducing interaction is big, the liquid beyond mixed liquor, water for the liquid beyond water and water,
Effect with reduction interaction.Thereby, it is possible to increase contact angle of the liquid to article surface.
The silicon compound A represented as above-mentioned formula [1], for example, CH can be enumerated3Si(OCH3)3、C2H5Si(OCH3)3、
C3H7Si(OCH3)3、C4H9Si(OCH3)3、C5H11Si(OCH3)3、C6H13Si(OCH3)3、C7H15Si(OCH3)3、C8H17Si
(OCH3)3、C9H19Si(OCH3)3、C10H21Si(OCH3)3、C11H23Si(OCH3)3、C12H25Si(OCH3)3、C13H27Si(OCH3)3、
C14H29Si(OCH3)3、C15H31Si(OCH3)3、C16H33Si(OCH3)3、C17H35Si(OCH3)3、C18H37Si(OCH3)3、(CH3)2Si
(OCH3)2、C2H5Si(CH3)(OCH3)2、(C2H5)2Si(OCH3)2、C3H7Si(CH3)(OCH3)2、(C3H7)2Si(OCH3)2、
C4H9Si(CH3)(OCH3)2、(C4H9)2Si(OCH3)2、C5H11Si(CH3)(OCH3)2、C6H13Si(CH3)(OCH3)2、C7H15Si
(CH3)(OCH3)2、C8H17Si(CH3)(OCH3)2、C9H19Si(CH3)(OCH3)2、C10H21Si(CH3)(OCH3)2、C11H23Si
(CH3)(OCH3)2、C12H25Si(CH3)(OCH3)2、C13H27Si(CH3)(OCH3)2、C14H29Si(CH3)(OCH3)2、C15H31Si
(CH3)(OCH3)2、C16H33Si(CH3)(OCH3)2、C17H35Si(CH3)(OCH3)2、C18H37Si(CH3)(OCH3)2、(CH3)3SiOCH3、C2H5Si(CH3)2OCH3、(C2H5)2Si(CH3)OCH3、(C2H5)3SiOCH3、C3H7Si(CH3)2OCH3、(C3H7)2Si
(CH3)OCH3、(C3H7)3SiOCH3、C4H9Si(CH3)2OCH3、(C4H9)3SiOCH3、C5H11Si(CH3)2OCH3、C6H13Si(CH3)2OCH3、C7H15Si(CH3)2OCH3、C8H17Si(CH3)2OCH3、C9H19Si(CH3)2OCH3、C10H21Si(CH3)2OCH3、C11H23Si
(CH3)2OCH3、C12H25Si(CH3)2OCH3、C13H27Si(CH3)2OCH3、C14H29Si(CH3)2OCH3、C15H31Si(CH3)2OCH3、
C16H33Si(CH3)2OCH3、C17H35Si(CH3)2OCH3、C18H37Si(CH3)2OCH3、(CH3)2Si(H)OCH3、CH3Si(H)2OCH3、(C2H5)2Si(H)OCH3、C2H5Si(H)2OCH3、C2H5Si(CH3)(H)OCH3、(C3H7)2Si(H)OCH3Deng alkyl methoxy
Base silane or CF3CH2CH2Si(OCH3)3、C2F5CH2CH2Si(OCH3)3、C3F7CH2CH2Si(OCH3)3、C4F9CH2CH2Si
(OCH3)3、C5F11CH2CH2Si(OCH3)3、C6F13CH2CH2Si(OCH3)3、C7F15CH2CH2Si(OCH3)3、C8F17CH2CH2Si
(OCH3)3、CF3CH2CH2Si(CH3)(OCH3)2、C2F5CH2CH2Si(CH3)(OCH3)2、C3F7CH2CH2Si(CH3)(OCH3)2、
C4F9CH2CH2Si(CH3)(OCH3)2、C5F11CH2CH2Si(CH3)(OCH3)2、C6F13CH2CH2Si(CH3)(OCH3)2、
C7F15CH2CH2Si(CH3)(OCH3)2、C8F17CH2CH2Si(CH3)(OCH3)2、CF3CH2CH2Si(CH3)2OCH3、C2F5CH2CH2Si
(CH3)2OCH3、C3F7CH2CH2Si(CH3)2OCH3、C4F9CH2CH2Si(CH3)2OCH3、C5F11CH2CH2Si(CH3)2OCH3、
C6F13CH2CH2Si(CH3)2OCH3、C7F15CH2CH2Si(CH3)2OCH3、C8F17CH2CH2Si(CH3)2OCH3、CF3CH2CH2Si
(CH3)(H)OCH3Deng fluothane methoxylsilane or by abovementioned alkyl methoxy silane or above-mentioned fluothane methoxylsilane
Methoxyl group methyl moiety be replaced to carbon number be 2~18 1 valency alkyl alkoxysilane compound containing trialkylsilyl group in molecular structure or will be above-mentioned
Methoxy substitution is into-OC (CH3)=CHCOCH3、-OC(CH3)=N-Si (CH3)3、-OC(CF3)=N-Si (CH3)3、-O-CO-
R20(R20Be part or all of protium optionally by 1 valency alkyl that the substituted carbon number such as fluorine element is 1~18), one
Point or whole protium optionally by the substituted alkyl sulfonic acid ester group such as fluorine element, NCO, amino, dialkyl amido, different
Thiocyanate groups, azido, acetamido ,-N (CH3)C(O)CH3、-N(CH3)C(O)CF3,-N=C (CH3)OSi(CH3)3、-N
=C (CF3)OSi(CH3)3、-NHC(O)-OSi(CH3)3、-NHC(O)-NH-Si(CH3)3, imidazole ring, oxazolidones ring, morpholine
Ring ,-NH-C (O)-Si (CH3)3、-N(H)2-i(Si(H)jR19 3-j)i(R19Optionally taken for part or all of protium by fluorine element
The carbon number in generation is 1~18 1 valency alkyl, the integer that i is 1 or 2, j are 0~2), chloro, bromo, iodo, itrile group or-CO-
NH-Si(CH3)3Compound etc..
If in addition, in above-mentioned formula [1] the silicon compound A that 4-a-b is represented X1Number be 1, then can be formed in heterogeneity
Above-mentioned water repellency overlay film, thus more preferably.
R in above-mentioned formula [1]1It is each independently of the others, optionally to be taken selected from part or all of protium by fluorine element
The carbon number in generation is at least one kind of group in 1~18 1 valency alkyl, is more preferably selected from CmH2m+1(m=1~18) and
CnF2n+1CH2CH2, can when forming water repellency overlay film on above-mentioned relief pattern surface during at least one kind of group in (n=1~8)
Further reduce the wettability of the surface, i.e. more excellent water repellency can be assigned to the surface, thus more preferably.If in addition,
M is that 1~12, n is 1~8, then can form water repellency overlay film on above-mentioned relief pattern surface with the short time, thus more preferably.
Wherein, above-mentioned silicon compound A is particularly preferably HMDS, trimethyl silyl dimethyl amine, three
Methyl silicane base diethylamide, tetramethyl-disilazane, dimetylsilyl dimethyl amine, dimetylsilyl diethyl
Base amine, 1,3- dibutyl tetramethyl-disilazane, Butyldimethylsilyl dimethyl amine, Butyldimethylsilyl two
Ethylamine, 1,3- dihexyls tetramethyl-disilazane, hexyl dimetylsilyl dimethyl amine, hexyl dimetylsilyl
Diethylamide, 1,3- dioctyls tetramethyl-disilazane, octyldimethyl silicyl dimethyl amine, octyldimethyl monosilane
Base diethylamide, 1,3- didecyls tetramethyl-disilazane, decyl dimethyl silicyl dimethyl amine, decyl dimethyl first silicon
Alkyl diethyl amine, 1,3- bis- (dodecyl) tetramethyl-disilazane, dodecyl dimethyl silicyl dimethyl amine, ten
Dialkyl dimethyl silicyl diethylamide.
In addition, above-mentioned acid is preferably selected from the sulfonic acid represented by hydrogen chloride, sulfuric acid, perchloric acid, phosphoric acid, above-mentioned formula [2]
And its carboxylic acid and its acid anhydrides, boron alkyl acid esters, aryl-boric acid ester, three (trifluoroacetyl epoxides) of acid anhydrides, above-mentioned formula [3] expression
It is at least one kind of in the group for the silicon compound B compositions that boron, tri-alkoxy boroxin, boron trifluoride, above-mentioned formula [4] are represented.
The sulfonic acid and its acid anhydrides represented as above-mentioned formula [2], there is methanesulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, fluoroform sulphur
Acid, trifluoromethanesulfanhydride anhydride etc., as above-mentioned formula [3] represent carboxylic acid and its acid anhydrides, have acetic acid, trifluoroacetic acid, five fluorine propionic acid,
Acetic anhydride, TFAA, PFPA etc., preferably the silicon compound B represented as above-mentioned formula [4], chlorosilane, alkane
Base silylalkyl sulphonic acid ester, alkylsilyl groups base ester, there is trimethyl silyl trifluoro-acetate, trimethyl silyl
Triflate, dimetylsilyl trifluoro-acetate, dimetylsilyl triflate, butyldimethyl
Silylation trifluoro-acetate, Butyldimethylsilyl triflate, hexyl dimetylsilyl trifluoro-acetate,
Hexyl dimetylsilyl triflate, octyldimethyl silicyl trifluoro-acetate, octyldimethyl monosilane
Base triflate, decyl dimethyl silicyl trifluoro-acetate, decyl dimethyl silicyl triflate, ten
Dialkyl dimethyl silicyl trifluoro-acetate, dodecyl dimethyl silicyl triflate etc..
In addition, above-mentioned alkali is preferably selected from by ammonia, N, N, N ', N '-tetramethylethylenediamine, triethylenediamine, dimethylaniline,
The silicon compound C compositions that alkylamine, dialkylamine, trialkylamine, pyridine, piperazine, N- alkyl morpholines, above-mentioned formula [5] are represented
Group in it is at least one kind of.
By the above-mentioned acid or alkali included in chemical solution, above-mentioned silicon compound A can be promoted and as silicon systems chip
The reaction of the silanol group of the reaction site on surface, therefore by using the surface treatment of the chemical solution, can be brilliant to silicon systems
Piece surface assigns excellent water repellency.It should be noted that above-mentioned acid or alkali can also form a part for water repellency overlay film.
If reaction facilitation effect is considered, comprising acid preferably in above-mentioned chemical solution, wherein particularly preferably hydrogen chloride, sulphur
The bronsted acid of the strong acid such as acid, perchloric acid；Part or all of protium such as trifluoromethanesulfonic acid, trifluoromethanesulfanhydride anhydride is by fluorine member
The paraffin sulfonates and its acid anhydrides of element substitution；Part or all of protium quilt such as trifluoroacetic acid, TFAA, five fluorine propionic acid
The carboxylic acid and its acid anhydrides of fluorine element substitution；The aIkylsilyl groups that chlorosilane, part or all of protium are replaced by fluorine element
Alkyl sulfonic ester；The alkylsilyl groups base ester that part or all of protium is replaced by fluorine element.It should be noted that alkyl first
Silane base ester is that alkyl and-O-CO-R have been bonded on element silicon ' material of base (R ' be alkyl).It should be noted that chemical solution
The acid included in liquid can be by the acid of reaction generation, for example, reacting alkylchlorosilane and alcohol, by the alkyl alkoxy of generation
Silane is as silicon compound A, using the hydrochloric acid of generation as acid, using the alcohol not consumed in reaction as solvent, can also be refused
Aqueous chemical solution.
In addition, above-mentioned acid is preferably the silicon compound B that above-mentioned formula [4] represents, it is preferably selected from by trimethyl silyl
Base trifluoro-acetate, trimethylsilyl triflate, dimetylsilyl trifluoro-acetate, dimethyl silane
Base triflate, Butyldimethylsilyl trifluoro-acetate, Butyldimethylsilyl triflate, oneself
Base dimetylsilyl trifluoro-acetate, hexyl dimetylsilyl triflate, octyldimethyl silicyl
Trifluoro-acetate, octyldimethyl silicyl triflate, decyl dimethyl silicyl trifluoro-acetate, decyl two
Methyl silicane base triflate, dodecyl dimethyl silicyl trifluoro-acetate, dodecyl dimethyl first silicon
It is at least one kind of in the group of alkyl triflate composition.
The silicon compound B that above-mentioned formula [4] represents can also be obtained by reaction.For example, it is also possible to make following formulas
[16] the silicon compound D represented is made up of with being selected from trifluoroacetic acid, TFAA, trifluoromethanesulfonic acid, trifluoromethanesulfanhydride anhydride
The material obtained by least one kind of (following, be designated as sometimes " sour D ") reaction in group.
(R21)p(H)qSiX10 4-p-q [16]
(in formula [16], R21It is each independently of the others, for selected from CmH2m+1(m=1~18) and CnF2n+1CH2CH2(n=1~8)
In at least one kind of group, p is 1~3 integer, and q is 0~2 integer, and p and q's adds up to 1~3.X10It is each independently of the others,
Represent the 1 valency functional group that the element being bonded with element silicon is nitrogen.It is used as (R21)p(H)qSi-, can enumerate (CH3)3Si-、(CH3)2
(H)Si-、(C4H9)(CH3)2Si-、(C6H13)(CH3)2Si-、(C8H17)(CH3)2Si-、(C10H21)(CH3)2Si- and (C12H25)
(CH3)2Si- etc..
If for example, HMDS and TFAA as acid D of the mixing as silicon compound D, trifluoro
Acetic anhydride immediate response, can obtain the trimethyl silyl trifluoro-acetate as silicon compound B.
If in addition, for example, mixing as silicon compound D HMDS and the trifluoromethanesulfanhydride anhydride as acid D,
Then trifluoromethanesulfanhydride anhydride immediate response, can obtain the trimethylsilyl triflate as silicon compound B.
If in addition, for example, mixing as silicon compound D tetramethyl-disilazane and the TFAA as acid D,
TFAA immediate response, can obtain the dimetylsilyl trifluoro-acetate as silicon compound B.
If in addition, for example, mixing as silicon compound D tetramethyl-disilazane and the trifluoromethanesulfanhydride anhydride as acid D,
Then trifluoromethanesulfanhydride anhydride immediate response, can obtain the dimetylsilyl triflate as silicon compound B.
If in addition, for example, mixing is used as silicon compound D 1,3- dibutyl tetramethyl-disilazane and three as acid D
Fluoroacetic acid acid anhydride, then TFAA immediate response, can obtain the Butyldimethylsilyl trifluoro second as silicon compound B
Acid esters.
If in addition, for example, mixing is used as silicon compound D 1,3- dibutyl tetramethyl-disilazane and three as acid D
Fluorine methanesulfonic acid acid anhydride, then trifluoromethanesulfanhydride anhydride immediate response, can obtain the Butyldimethylsilyl three as silicon compound B
Fluorine methanesulfonates.
If in addition, for example, mixing is used as silicon compound D 1,3- dioctyls tetramethyl-disilazane and three as acid D
Fluoroacetic acid acid anhydride, then TFAA immediate response, can obtain the octyldimethyl silicyl trifluoro second as silicon compound B
Acid esters.
If in addition, for example, mixing is used as silicon compound D 1,3- dioctyls tetramethyl-disilazane and three as acid D
Fluorine methanesulfonic acid acid anhydride, then trifluoromethanesulfanhydride anhydride immediate response, can obtain the octyldimethyl silicyl three as silicon compound B
Fluorine methanesulfonates.
If in addition, for example, mixing is used as silicon compound D 1,3- didecyls tetramethyl-disilazane and three as acid D
Fluoroacetic acid acid anhydride, then TFAA immediate response, can obtain the decyl dimethyl silicyl trifluoro second as silicon compound B
Acid esters.
If in addition, for example, mixing is used as silicon compound D 1,3- didecyls tetramethyl-disilazane and three as acid D
Fluorine methanesulfonic acid acid anhydride, then trifluoromethanesulfanhydride anhydride immediate response, can obtain the decyl dimethyl silicyl three as silicon compound B
Fluorine methanesulfonates.
If in addition, for example, mixing as silicon compound D octyldimethyl silicyl dimethyl amine and be used as acid D's
TFAA, then TFAA immediate response, can obtain the octyldimethyl silicyl trifluoro as silicon compound B
Acetic acid esters.
If in addition, for example, mixing as silicon compound D decyl dimethyl silicyl dimethyl amine and be used as acid D's
TFAA, then TFAA immediate response, can obtain the decyl dimethyl silicyl trifluoro as silicon compound B
Acetic acid esters.
It should be noted that acid D using at least one kind of in TFAA and trifluoromethanesulfanhydride anhydride, make its with it is upper
State silicon compound D reactions and obtain silicon compound B, the silicon systems chip water repellency chemical solution that thus prepares or by above-mentioned silicon
Compound A and silicon compound B is used as the excellent in stability of the silicon systems chip water repellency chemical solution prepared by initiation material, because
And more preferably.
On the silicon systems chip water repellency chemical solution of the present invention, above-mentioned silication is excessively added relative to above-mentioned sour D
Compound D, the silicon compound D not consumed in above-mentioned reaction remainder can also contribute to above-mentioned as silicon compound A
The formation of water repellency overlay film.It should be noted that it is preferred that making above-mentioned silicon compound D mole of the molal quantity relative to above-mentioned sour D
Number is 0.2~100000 times, more preferably preferably 0.5~50000 times, 1~10000 times.
As long as it should be noted that the silicon compound B of above-mentioned formula [4] expression can be obtained, then can also utilize above-mentioned
Reaction beyond silicon compound D and above-mentioned sour D reaction.
It is used as the X of above-mentioned formula [16]10The element being bonded with element silicon can not only be included for 1 valency functional group of nitrogen
Hydrogen, carbon, nitrogen, oxygen, can also include the elements such as silicon, sulphur, halogen.It is used as the 1 valency functional group that the element being bonded with element silicon is nitrogen
Example, have NCO, amino, dialkyl amido, isothiocyanate group, azido, acetamido ,-N (CH3)C(O)
CH3、-N(CH3)C(O)CF3,-N=C (CH3)OSi(CH3)3,-N=C (CF3)OSi(CH3)3、-NHC(O)-OSi(CH3)3、-NHC
(O)-NH-Si(CH3)3, imidazole ring, oxazolidones ring, morpholine ring ,-NH-C (O)-Si (CH3)3、-N(H)2-i(Si(H)jR19 3-j)i
(R19Be part or all of protium optionally by the 1 valency alkyl that the carbon number that fluorine element replaces is 1~18, i is 1 or 2, j are
0~2 integer) etc..
As the silicon compound D of above-mentioned formula [16], for example, (CH can be enumerated3)3SiNH2、C4H9Si(CH3)2NH2、
C6H13Si(CH3)2NH2、C8H17Si(CH3)2NH2、C10H21Si(CH3)2NH2、C12H25Si(CH3)2NH2、(CH3)2Si(H)NH2's
Amino silane or the amino (- NH by above-mentioned amino silane2Base) it is replaced to-N=C=O ,-N (CH3)2、-N(C2H5)2,-N=
C=S ,-N3、-NHC(O)CH3、-N(CH3)C(O)CH3、-N(CH3)C(O)CF3,-N=C (CH3)OSi(CH3)3,-N=C (CF3)
OSi(CH3)3、-NHC(O)-OSi(CH3)3、-NHC(O)-NH-Si(CH3)3, imidazole ring, oxazolidones ring, morpholine ring ,-NH-C
(O)-Si(CH3)3、-NH-Si(CH3)3、-NH-Si(H)(CH3)2、-NH-Si(CH3)2(C4H9)、-NH-Si(CH3)2(C6H13)、-
NH-Si(CH3)2(C8H17)、-NH-Si(CH3)2(C10H21)、-NH-Si(CH3)2(C12H25)、-NH-Si(CH3)2
(C2H4C6F13)、-N-{Si(CH3)3}2Compound etc..
Wherein, the silicon compound D of above-mentioned formula [16] is preferably above-mentioned silicon compound A.
In above-mentioned silicon systems chip with water repellency chemical solution, silicon compound B concentration is closed preferably with respect to above-mentioned silication
The thing A mass % of total amount 100 is 0.01~20 mass %.If the concentration is low, silicon compound B effect is low, thus not preferably,
Even if the excessive concentration, silicon compound B effect can not also be improved, on the contrary it is also possible to corroding silicon systems wafer surface.Therefore,
Total amount 100 mass % of the above-mentioned silicon compound B concentration particularly preferably relative to above-mentioned silicon compound A is 0.05~15 matter
Measure %.
In addition, in above-mentioned silicon systems chip with water repellency chemical solution, above-mentioned silicon compound A and silicon compound B can be with
By organic solvent diluting.Relative to the mass % of total amount 100 of above-mentioned silicon systems chip water repellency chemical solution, if making silicon compound
The summation of A and silicon compound B addition is 0.1~100 mass %, then easily at least recess surface of above-mentioned relief pattern
Water repellency overlay film is formed uniformly, thus preferably.If less than 0.1 mass %, the protecting effect with relief pattern is insufficient
Tendency.More preferably 0.5~50 mass %, more preferably 1~30 mass %.It should be noted that silicon systems chip is used
In the case that water repellency chemical solution is by organic solvent diluting, as organic solvent, lower boiling material can be included, but it is heavy
Want, in the silicon systems chip with the boiling point for measuring most compositions in composition contained in water repellency chemical solution by quality ratio
More than 40 DEG C.More preferably above 60 DEG C of the boiling point, further preferably more than 80 DEG C.
As in the above-mentioned silicon systems chip organic solvent for being used to dilute in water repellency chemical solution, for example, suitably using
It is hydro carbons, esters, ethers, ketone, the solvent containing halogens, sulfoxide series solvent, interior ester series solvent, carbonate-based solvent, polynary
In the derivative of alcohol the organic solvent such as the material without OH bases, solvent of Nitrogen element without N-H bases or they
Mixed liquor.Wherein, if using in hydro carbons, esters, ethers, the solvent containing halogens, the derivative of polyalcohol do not have OH bases
Material or their mixed liquor, then water repellency overlay film can be formed on above-mentioned relief pattern surface with the short time, thus more
It is preferred that.
As the example of above-mentioned hydro carbons, there are toluene, benzene, dimethylbenzene, hexane, heptane, octane etc., be used as the example of above-mentioned esters
Son, there is ethyl acetate, propyl acetate, butyl acetate, ethyl acetoacetate etc., as the example of above-mentioned ethers, have Anaesthetie Ether,
Dipropyl ether, dibutyl ethers, tetrahydrofuran, dioxanes etc., as the example of above-mentioned ketone, there is acetone, acetylacetone,2,4-pentanedione, methyl second
Base ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone etc., as the example of the above-mentioned solvent containing halogens,
There are the perfluocarbons such as PFO, Perfluorononane, Decafluorocyclopentane, perfluorocyclohexane, phenyl-hexafluoride；The fluorine fourths of 1,1,1,3,3- five
The HFCs such as alkane, Octafluorocyclopentane, 2,3- dihydros Decafluoropentane, Zeorora H (ZEON CORPORATION systems)；Methyl perfluoro
Isobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethylperfluoro isobutyl ether, the ASAHIKLIN AE-3000 (rising suns
Nitre subsidiary system), the hydrofluoroether such as Novec7100, Novec7200, Novec7300, Novec7600 (being 3M systems)；Four chloromethanes
The chlorocarbons such as alkane；The hydrogeneous chlorinated hydrocabon such as chloroform；The CFC such as dicholorodifluoromethane；The chloro- 2,2,3,3,3- pentafluoropropanes of 1,1- bis-, 1,
The hydrogeneous chlorine such as the chloro- 1,1,2,2,3- pentafluoropropanes of 3- bis-, the chloro- 3,3,3- trifluoro propenes of 1-, the chloro- 3,3,3- trifluoro propenes of 1,2- bis-
Fluorohydrocarbon；Perfluoroether, PFPE etc., as the example of above-mentioned sulfoxide series solvent, there is dimethyl sulfoxide (DMSO) etc., are used as above-mentioned lactone system
The example of solvent, have gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, γ-heptalactone, γ-octalactone, nonyl lactone, γ-
Decalactone, gamma-undecalactone, γ-dodecalactone, δ-valerolactone, δ-caprolactone, δ-octalactone, δ-nonalactone, δ-decalactone,
Delta-undeca lactone, δ-dodecalactone, 6-caprolactone etc., as the example of above-mentioned carbonate-based solvent, there is dimethyl carbonate, carbonic acid
Methyl ethyl ester, diethyl carbonate, propene carbonate etc., are used as the example of the material without OH bases in the derivative of above-mentioned polyalcohol
Son, there is ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol dibutyl ethers, ethylene glycol single methyl ether acetic acid esters, ethylene glycol
Single monoethyl ether acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene acetate, diethylene glycol dimethyl ether, diethylene glycol
Ethyl-methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol list first
Base ether acetic acid ester, TC acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, diethylene glycol diacetate esters, three
Ethylene glycol dimethyl ether, triethylene glycol Anaesthetie Ether, triethylene glycol dibutyl ethers, triethylene glycol butyl methyl ether, triethylene glycol
Monomethyl ether acetate, triethylene glycol monoethyl ether acetic acid ester, triethylene glycol monobutyl base ether acetic acid ester, triethylene glycol oxalic acid
Ester, tetraethylene glycol dimethyl ether, tetraethylene glycol Anaesthetie Ether, tetraethylene glycol dibutyl ethers, tetraethylene glycol monomethyl ether acetate,
Tetraethylene glycol list monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate esters, propane diols dimethyl
Ether, propane diols Anaesthetie Ether, propane diols dibutyl ethers, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, third
Glycol monobutyl ether acetate, propylene-glycol diacetate, dipropylene glycol dimethyl, dipropylene glycol methyl-propyl
Ether, dipropylene glycol Anaesthetie Ether, dipropylene glycol dibutyl ethers, dipropylene glycol monomethyl ether acetate, a contracting
Dihydroxypropane single-ethyl ether acetic acid esters, dipropylene glycol monobutyl base ether acetic acid ester, dipropylene glycol diacetate esters, 3 the third two
Alcohol dimethyl ether, tripropylene glycol Anaesthetie Ether, tripropylene glycol dibutyl ethers, tripropylene glycol monomethyl ether acetate, tripropylene glycol
Single monoethyl ether acetate, tripropylene glycol monobutyl base ether acetic acid ester, tripropylene glycol diacetate esters, four propylene glycol dimethyl ethers, 4 third
Glycol monomethyl ether acetic acid esters, four propylene-glycol diacetates, butanediol dimethyl ether, butanediol monomethyl ether acetate, fourth two
Alcohol diacetate esters, glycerol triacetate etc., as the example of the solvent of the above-mentioned Nitrogen element without N-H bases, there is N, N- bis-
NMF, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, triethylamine, pyridine etc..
If in addition, part or all of above-mentioned solvent uses non-flame properties material, silicon systems chip water repellency chemistry
Solution becomes noninflammability, or flash-point rise, and the silicon systems chip is reduced with the danger of water repellency chemical solution, thus preferably.
Solvent containing halogens is generally noninflammability, and it is organic molten that the non-flame properties solvent containing halogens can be suitable for use as noninflammability
Agent.
If in addition, using solvent of the flash-point more than 70 DEG C as above-mentioned solvent, coming from the viewpoint of the security in fire service law
See preferably.
In addition, according to " GHS：GHS ", flash-point is determined for less than 93 DEG C of solvent
Justice is " flammable liquid ".Therefore, even if not being noninflammability solvent, if using solvent of the flash-point more than 93 DEG C as above-mentioned solvent,
The flash-point of above-mentioned water repellency chemical solution is also well over 93 DEG C, because the chemical solution is difficult to meet " flammable liquid ", thus
It is further preferred from a security point of view.
In addition, the material without OH bases is generally flash-point in the derivative of interior ester series solvent, carbonate-based solvent, polyalcohol
High material, therefore, it is possible to reduce the danger of silicon systems chip water repellency chemical solution, thus preferably.From above-mentioned security
From the point of view of viewpoint, specifically, more preferably using flash-point more than 70 DEG C of gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, γ-heptan
Lactone, γ-octalactone, nonyl lactone, γ-decalactone, gamma-undecalactone, γ-dodecalactone, δ-valerolactone, δ-caprolactone,
δ-octalactone, δ-nonalactone, δ-decalactone, delta-undeca lactone, δ-dodecalactone, 6-caprolactone, propene carbonate, ethylene glycol two
Butyl ether, ethylene glycol monobutyl ether acetic acid esters, ethylene acetate, diethylene glycol ethyl methyl ether, diethylene glycol diethyl
Ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol mono-ethyl
Ether acetic acid ester, diethylene glycol monobutyl ether acetic acid esters, diethylene glycol diacetate esters, triethylene glycol dimethyl ether, triethylene glycol two
Ethylether, triethylene glycol dibutyl ethers, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol list
Monoethyl ether acetate, triethylene glycol monobutyl base ether acetic acid ester, triethylene glycol diacetate esters, tetraethylene glycol dimethyl ether, tetrem two
Alcohol Anaesthetie Ether, tetraethylene glycol dibutyl ethers, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol list monoethyl ether acetate, four
Ethylene glycol monobutyl ether acetic acid esters, tetraethylene glycol diacetate esters, propylene-glycol diacetate, dipropylene glycol methyl-propyl ether,
Dipropylene glycol monomethyl ether acetate, dipropylene glycol list monoethyl ether acetate, dipropylene glycol monobutyl base ether second
Acid esters, dipropylene glycol diacetate esters, tripropylene glycol dimethyl, tripropylene glycol Anaesthetie Ether, tripropylene glycol dibutyl ethers,
Tripropylene glycol monomethyl ether acetate, tripropylene glycol list monoethyl ether acetate, tripropylene glycol monobutyl base ether acetic acid ester, tripropylene glycol
Diacetate esters, four propylene glycol dimethyl ethers, four propylene glycol monomethyl ethers, four propylene-glycol diacetates, butanediol diethyl
Acid esters, glycerol triacetate etc. as above-mentioned solvent, further preferably using gamma-butyrolacton of the flash-point more than 93 DEG C, γ-oneself in
Ester, γ-heptalactone, γ-octalactone, nonyl lactone, γ-decalactone, gamma-undecalactone, γ-dodecalactone, δ-valerolactone,
δ-caprolactone, δ-octalactone, δ-nonalactone, δ-decalactone, delta-undeca lactone, δ-dodecalactone, 6-caprolactone, propylene carbonate
Ester, ethylene acetate, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol diacetate esters, diethyl two
Alcohol monomethyl ether acetate, TC acetic acid esters, diethylene glycol monobutyl ether acetic acid esters, triethylene glycol dimethyl
Ether, triethylene glycol Anaesthetie Ether, triethylene glycol dibutyl ethers, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether
Ester, triethylene glycol monoethyl ether acetic acid ester, triethylene glycol monobutyl base ether acetic acid ester, triethylene glycol diacetate esters, tetraethylene glycol two
Methyl ether, tetraethylene glycol Anaesthetie Ether, tetraethylene glycol dibutyl ethers, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol list second
Base ether acetic acid ester, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate esters, propylene-glycol diacetate, a contracting dipropyl two
Alcohol diacetate esters, dipropylene glycol monomethyl ether acetate, dipropylene glycol list monoethyl ether acetate, dipropylene glycol
Monobutyl ether acetate, tripropylene glycol dimethyl, tripropylene glycol Anaesthetie Ether, tripropylene glycol dibutyl ethers, tripropylene glycol list
Methylether acetate, tripropylene glycol list monoethyl ether acetate, tripropylene glycol monobutyl base ether acetic acid ester, tripropylene glycol diacetate esters,
Four propylene glycol dimethyl ethers, four propylene glycol monomethyl ethers, four propylene-glycol diacetates, butanediol diacetate esters, glycerine
Triacetate etc. is used as above-mentioned solvent.
In addition, to above-mentioned silicon systems chip with for water repellency chemical solution, the total amount of the moisture in initiation material relative to
The total amount of the raw material is preferably below 5000 mass ppm.In the case that the total amount of moisture is more than 5000 mass ppm, above-mentioned silication
Compound A effect reduction, it is difficult to which above-mentioned water repellency overlay film is formed with the short time.Therefore, above-mentioned silicon systems chip water repellency chemistry
Amount of moisture in the initiation material of solution is more few more preferred, particularly preferably below 1000 mass ppm, more preferably 500
Below quality ppm.As long as it should be noted that amount of moisture of the above-mentioned silicon systems chip in the initiation material of water repellency chemical solution
Within the above range, then it can be more than 5 mass ppm.
Hereinafter, the 2nd method is illustrated.Above-mentioned metal system chip is included with water repellency chemical solution and is selected from above-mentioned formula
[6]~[12] compound and its at least one kind of compound and solvent in salt compound represented.
The R of above-mentioned formula [6]8For example, alkyl, alkylidene or they part or all for the alkyl of expression
Group that protium is replaced by fluorine element etc..
In addition, the R of above-mentioned formula [6]9In contained alkyl can for example enumerate alkyl, alkylidene or their part
Or the group that is replaced by fluorine element of whole protiums etc..Additionally, it is preferred that being-OR22(R22It is the alkyl that carbon number is 1~18).
If in addition, R22Carbon number for 1~8, particularly 1~4, then can assign more excellent water repellency, thus preferably.In addition,
R22Preferably straight chained alkyl.
As the compound of the phosphorus element-containing of above-mentioned formula [6], for example, CH can be enumerated3P(O)(OH)2、C2H5P(O)
(OH)2、C3H7P(O)(OH)2、C4H9P(O)(OH)2、C5H11P(O)(OH)2、C6H13P(O)(OH)2、C7H15P(O)(OH)2、
C8H17P(O)(OH)2、C9H19P(O)(OH)2、C10H21P(O)(OH)2、C11H23P(O)(OH)2、C12H25P(O)(OH)2、C13H27P
(O)(OH)2、C14H29P(O)(OH)2、C15H31P(O)(OH)2、C16H33P(O)(OH)2、C17H35P(O)(OH)2、C18H37P(O)
(OH)2、C6H5P(O)(OH)2、CF3P(O)(OH)2、C2F5P(O)(OH)2、C3F7P(O)(OH)2、C4F9P(O)(OH)2、C5F11P
(O)(OH)2、C6F13P(O)(OH)2、C7F15P(O)(OH)2、C8F17P(O)(OH)2、CF3C2H4P(O)(OH)2、C2F5C2H4P(O)
(OH)2、C3F7C2H4P(O)(OH)2、C4F9C2H4P(O)(OH)2、C5F11C2H4P(O)(OH)2、C6F13C2H4P(O)(OH)2、
C7F15C2H4P(O)(OH)2、C8F17C2H4P(O)(OH)2Or by the-P (O) (OH) of above-claimed cpd2Base is replaced to-P (O)
(OH)OCH3Base ,-P (O) (OH) OC2H5Base ,-P (O) (OCH3)2Base ,-P (O) (OC2H5)2Compound of base etc..
In addition, the compound of the phosphorus element-containing of above-mentioned formula [6] can assign more excellent water repellency, therefore above-mentioned formula
[6] g is preferably 1 or 2, the compound that following formulas [17] that further preferred g is 2 are represented.
R23- P (=O) (OH)2 [17]
(in formula [17], R23It is part or all of protium optionally by the carbon number that fluorine element replaces is 1~18 1
Valency alkyl.)
The R of above-mentioned formula [6]8With the R of above-mentioned formula [17]23The protium quilt of alkyl, phenyl, phenyl can for example be enumerated
Group that part or all of protium of alkyl-substituted group, naphthyl and these alkyl is replaced by fluorine element etc..
If in addition, the R of above-mentioned formula [6]8With the R of above-mentioned formula [17]23Carbon number for 2~16, particularly 4~
14 and then for 6~14, then more excellent water repellency can be assigned, thus preferably.In addition, part or all of above-mentioned protium
The alkyl preferably alkyl optionally replaced by fluorine element, particularly preferably straight chained alkyl.If above-mentioned alkyl is straight chained alkyl,
When forming water repellency overlay film, the hydrophobic portion of the compound for the phosphorus element-containing that formula [6] and [17] are represented is R8And R23Relative to this
The surface of water repellency overlay film is easily arranged towards vertical direction, therefore the effect of imparting water repellency is further improved, thus more excellent
Choosing.In addition, above-mentioned R8And R23More excellent water repellency can be assigned, therefore preferably part or all of protium is taken by fluorine element
The alkyl in generation.
In addition, the compound of above-mentioned phosphorus element-containing can exist in the form of above-mentioned formula [6] or the salt of [17].It is used as this
Salt, there is ammonium salt or amine salt etc..
In addition, the R of above-mentioned formula [7]10, formula [8] R11, formula [9] R14, formula [10] R15, formula [11]
R16With the R of formula [12]17With R18The carbon number that preferably part or all of protium is optionally replaced by fluorine element for 1~
18 1 valency alkyl, more preferably CmH2m+1(m=1~18), CnF2n+1CH2CH2(n=1~8), CrF2r+1CH2(r=1~
8)、CsF2s+1(s=1~8).
The compound represented as above-mentioned formula [7], for example, CH can be enumerated3COCl、C2H5COCl、C3H7COCl、
C4H9COCl、C5H11COCl、C6H13COCl、C7H15COCl、C8H17COCl、C9H19COCl、C10H21COCl、C11H23COCl、
C12H25COCl、C13H27COCl、C14H29COCl、C15H31COCl、C16H33COCl、C17H35COCl、C18H37COCl、C6H5COCl、
CF3COCl、C2F5COCl、C3F7COCl、C4F9COCl、C5F11COCl、C6F13COCl、C7F15COCl、C8F17COCl or by it
- Cl bases be replaced to-F bases ,-Br bases, compound of-I bases etc..
In above-mentioned compound, it is contemplated that compatibility to the material comprising metal series elements and to metal system chip table
The water repellency in face assigns effect, and particularly preferred compound can for example enumerate C8H17COCl、C9H19COCl、C10H21COCl、
C11H23COCl、C12H25COCl、C13H27COCl、C14H29COCl、C15H31COCl、C16H33COCl、C17H35COCl、C18H37COCl、
C4F9COCl、C5F11COCl、C6F13COCl、C7F15COCl、C8F17COCl etc..
The compound represented as above-mentioned formula [8], for example, C can be enumerated5H11NH2、C6H13NH2、C7H15NH2、
C8H17NH2、C9H19NH2、C10H21NH2、C11H23NH2、C12H25NH2、C13H27NH2、C14H29NH2、C15H31NH2、C16H33NH2、
C17H35NH2、C18H37NH2、CF3NH2、CF3C2H4NH2、C2F5NH2、C2F5C2H4NH2、C3F7NH2、C3F7C2H4NH2、C4F9NH2、
C4F9C2H4NH2、C4F9CH2NH2、C5F11NH2、C5F11C2H4NH2、C5F11CH2NH2、C6F13NH2、C6F13C2H4NH2、
C6F13CH2NH2、C7F15NH2、C7F15C2H4NH2、C7F15CH2NH2、C8F17NH2、C8F17C2H4NH2、C8F17CH2NH2、C4F7H2NH2、
C6F11H2NH2、C8F15H2NH2、(C3H7)2NH、(C4H9)2NH、(C5H11)2NH、(C6H13)2NH、(C7H15)2NH、(C8H17)2NH、
(C9H19)2NH、(C10H21)2NH、(C11H23)2NH、(C12H25)2NH、(C13H27)2NH、(C14H29)2NH、(C15H31)2NH、
(C16H33)2NH、(C17H35)2NH、(C18H37)2NH、(CF3)2NH、(C2F5)2NH、(C3F7)2NH、(C4F9)2NH、(C5F11)2NH、
(C6F13)2NH、(C7F15)2NH、(C8F17)2NH、(C4F7H2)2NH、(C6F11H2)2NH、(C8F15H2)2NH、(C2H5)3N、(C3H7)3N、(C4H9)3N、(C5H11)3N、(C6H13)3N、(C7H15)3N、(C8H17)3N、(C9H19)3N、(C10H21)3N、(C11H23)3N、
(C12H25)3N、(C13H27)3N、(C14H29)3N、(C15H31)3N、(C16H33)3N、(C17H35)3N、(C18H37)3N、(CF3)3N、
(C2F5)3N、(C3F7)3N、(C4F9)3N、(C5F11)3N、(C6F13)3N、(C7F15)3N、(C8F17)3N、(C4F7H2)3N、(C6F11H2)3N、(C8F15H2)3N、(C5H11)(CH3)NH、(C6H13)(CH3)NH、(C7H15)(CH3)NH、(C8H17)(CH3)NH、(C9H19)
(CH3)NH、(C10H21)(CH3)NH、(C11H23)(CH3)NH、(C12H25)(CH3)NH、(C13H27)(CH3)NH、(C14H29)(CH3)
NH、(C15H31)(CH3)NH、(C16H33)(CH3)NH、(C17H35)(CH3)NH、(C18H37)(CH3)NH、(CF3)(CH3)NH、
(C2F5)(CH3)NH、(C3F7)(CH3)NH、(C4F9)(CH3)NH、(C5F11)(CH3)NH、(C6F13)(CH3)NH、(C7F15)(CH3)
NH、(C8F17)(CH3)NH、(C3H7)(CH3)2N、(C4H9)(CH3)2N、(C5H11)(CH3)2N、(C6H13)(CH3)2N、(C7H15)
(CH3)2N、(C8H17)(CH3)2N、(C9H19)(CH3)2N、(C10H21)(CH3)2N、(C11H23)(CH3)2N、(C12H25)(CH3)2N、
(C13H27)(CH3)2N、(C14H29)(CH3)2N、(C15H31)(CH3)2N、(C16H33)(CH3)2N、(C17H35)(CH3)2N、(C18H37)
(CH3)2N、(CF3)(CH3)2N、(C2F5)(CH3)2N、(C3F7)(CH3)2N、(C4F9)(CH3)2N、(C5F11)(CH3)2N、(C6F13)
(CH3)2N、(C7F15)(CH3)2N、(C8F17)(CH3)2The compounds such as N.In addition, the compound that represents of above-mentioned formula [8] can be with
The form of salt is used.As the salt, the inorganic acid salts such as carbonate, hydrochloride, sulfate, nitrate can be enumerated；Acetate, third
The acylates such as hydrochlorate, butyrate, phthalate.
In above-mentioned compound, it is contemplated that compatibility to the material comprising metal series elements and to metal system chip table
The water repellency in face assigns effect, and particularly preferred compound can for example enumerate C6H13NH2、C7H15NH2、C8H17NH2、
C9H19NH2、C10H21NH2、C11H23NH2、C12H25NH2、C13H27NH2、C14H29NH2、C15H31NH2、C16H33NH2、C17H35NH2、
C18H37NH2、(C4H9)2NH、(C5H11)2NH、(C6H13)2NH、(C7H15)2NH、(C8H17)2NH、(C9H19)2NH、(C10H21)2NH、
(C11H23)2NH、(C12H25)2NH、(C13H27)2NH、(C14H29)2NH、(C15H31)2NH、(C16H33)2NH、(C17H35)2NH、
(C18H37)2NH、(C4H9)3N、(C5H11)3N、(C6H13)3N、(C7H15)3N、(C8H17)3N、(C9H19)3N、(C10H21)3N、
(C11H23)3N、(C12H25)3N、(C13H27)3N、(C14H29)3N、(C15H31)3N、(C16H33)3N、(C17H35)3N、(C18H37)3N、
(C5H11)(CH3)NH、(C6H13)(CH3)NH、(C7H15)(CH3)NH、(C8H17)(CH3)NH、(C9H19)(CH3)NH、(C10H21)
(CH3)NH、(C11H23)(CH3)NH、(C12H25)(CH3)NH、(C13H27)(CH3)NH、(C14H29)(CH3)NH、(C15H31)(CH3)
NH、(C16H33)(CH3)NH、(C17H35)(CH3)NH、(C18H37)(CH3)NH、(C4H9)(CH3)2N、(C5H11)(CH3)2N、
(C6H13)(CH3)2N、(C7H15)(CH3)2N、(C8H17)(CH3)2N、(C9H19)(CH3)2N、(C10H21)(CH3)2N、(C11H23)
(CH3)2N、(C12H25)(CH3)2N、(C13H27)(CH3)2N、(C14H29)(CH3)2N、(C15H31)(CH3)2N、(C16H33)(CH3)2N、
(C17H35)(CH3)2N、(C18H37)(CH3)2N、C4F9NH2、C4F9C2H4NH2、C4F9CH2NH2、C5F11NH2、C5F11C2H4NH2、
C5F11CH2NH2、C6F13NH2、C6F13C2H4NH2、C6F13CH2NH2、C7F15NH2、C7F15C2H4NH2、C7F15CH2NH2、C8F17NH2、
C8F17C2H4NH2、C8F17CH2NH2Etc. compound.
The compound represented as above-mentioned formula [9], for example, C can be enumerated5H11COOH、C6H13COOH、C7H15COOH、
C8H17COOH、C9H19COOH、C10H21COOH、C11H23COOH、C12H25COOH、C13H27COOH、C14H29COOH、C15H31COOH、
C16H33COOH、C17H35COOH、C18H37COOH、C6H5COOH、C5F11COOH、C6F13COOH、C7F15COOH、C8F17COOH etc. changes
Compound or the-COOH bases of the compound are replaced to-COOCH3Base ,-COOC2H5Base ,-COOC6H5Base ,-COSH bases ,-
COSCH3Compound of base etc..
In above-mentioned compound, it is contemplated that compatibility to the material comprising metal series elements and to metal system chip table
The water repellency in face assigns effect, and particularly preferred compound can for example enumerate C5H11COOH、C6H13COOH、C7H15COOH、
C8H17COOH、C9H19COOH、C10H21COOH、C11H23COOH、C12H25COOH、C13H27COOH、C14H29COOH、C15H31COOH、
C16H33COOH、C17H35COOH、C18H37COOH or the-COOH bases of the compound are replaced to-COOCH3Base ,-COOC2H5
Base ,-COOC6H5Base ,-COSH bases ,-COSCH3Compound of base etc..
The compound represented as above-mentioned formula [10], for example, C can be enumerated2H5NCO、C3H7NCO、C4H9NCO、
C5H11NCO、C6H13NCO、C7H15NCO、C8H17NCO、C9H19NCO、C10H21NCO、C11H23NCO、C12H25NCO、C13H27NCO、
C14H29NCO、C15H31NCO、C16H33NCO、C17H35NCO、C18H37NCO、CF3NCO、CF3CH2NCO、CF3C2H4NCO、C2F5NCO、
C2F5CH2NCO、C2F5C2H4NCO、C3F7NCO、C3F7CH2NCO、C3F7C2H4NCO、C4F9NCO、C4F9CH2NCO、C4F9C2H4NCO、
C5F11NCO、C5F11CH2NCO、C5F11C2H4NCO、C6F13NCO、C6F13CH2NCO、C6F13C2H4NCO、C7F15NCO、
C7F15CH2NCO、C7F15C2H4NCO、C8F17NCO、C8F17CH2NCO、C8F17C2H4NCO、C2H4(NCO)2、C3H6(NCO)2、C4H8
(NCO)2、C5H10(NCO)2、C6H12(NCO)2、C7H14(NCO)2、C8H16(NCO)2、C9H18(NCO)2、C10H20(NCO)2、C11H22
(NCO)2、C12H24(NCO)2、C13H26(NCO)2、C14H28(NCO)2、C15H30(NCO)2、C16H32(NCO)2、C17H34(NCO)2、
C18H36(NCO)2、(NCO)C2H4NCO、(NCO)C3H6NCO、(NCO)C4H8NCO、(NCO)C5H10NCO、(NCO)C6H12NCO、
(NCO)C7H14NCO、(NCO)C8H16NCO、(NCO)C9H18NCO、(NCO)C10H20NCO、(NCO)C11H22NCO、(NCO)
C12H24NCO、(NCO)C13H26NCO、(NCO)C14H28NCO、(NCO)C15H30NCO、(NCO)C16H32NCO、(NCO)C17H34NCO、
(NCO)C18H36NCO、C2H3(NCO)3、C3H5(NCO)3、C4H7(NCO)3、C5H9(NCO)3、C6H11(NCO)3、C7H13(NCO)3、
C8H15(NCO)3、C9H17(NCO)3、C10H19(NCO)3、C11H21(NCO)3、C12H23(NCO)3、C13H25(NCO)3、C14H27
(NCO)3、C15H29(NCO)3、C16H31(NCO)3、C17H33(NCO)3、C18H35(NCO)3、C(NCO)4、(NCO)2C2H2(NCO)2、
(NCO)2C3H4(NCO)2、(NCO)2C4H6(NCO)2、(NCO)2C5H8(NCO)2、(NCO)2C6H10(NCO)2、(NCO)2C7H12
(NCO)2、(NCO)2C8H14(NCO)2、(NCO)2C9H16(NCO)2、(NCO)2C10H18(NCO)2、(NCO)2C11H20(NCO)2、
(NCO)2C12H22(NCO)2、(NCO)2C13H24(NCO)2、(NCO)2C14H26(NCO)2、(NCO)2C15H28(NCO)2、(NCO)2C16H30(NCO)2、(NCO)2C17H32(NCO)2、(NCO)2C18H34(NCO)2Deng isocyanate compound or by above-mentioned isocyanide
The NCO (- NCO bases) of ester compound is replaced to-SH bases ,-CHO bases ,-CONHOH bases, imidazoline ring (following formula [18])
Deng compound of ring structure comprising nitrogen etc..
[chemical formula 2]
In above-mentioned compound, it is contemplated that compatibility to the material comprising metal series elements and to metal system chip table
The water repellency in face assigns effect, and particularly preferred compound can for example enumerate C4H9NCO、C5H11NCO、C6H13NCO、
C7H15NCO、C8H17NCO、C9H19NCO、C10H21NCO、C11H23NCO、C12H25NCO、C13H27NCO、C14H29NCO、C15H31NCO、
C16H33NCO、C17H35NCO、C18H37NCO、C3F7CH2NCO、C3F7C2H4NCO、C4F9NCO、C4F9CH2NCO、C4F9C2H4NCO、
C5F11NCO、C5F11CH2NCO、C5F11C2H4NCO、C6F13NCO、C6F13CH2NCO、C6F13C2H4NCO、C7F15NCO、
C7F15CH2NCO、C7F15C2H4NCO、C8F17NCO、C8F17CH2NCO、C8F17C2H4Isocyanate compounds such as NCO or will be upper
The NCO (- NCO bases) for stating isocyanate compound is replaced to the bag such as-SH bases ,-CHO bases ,-CONHOH bases, imidazoline ring
Compound of the ring structure of Nitrogen element etc..
The compound represented as above-mentioned formula [11], for example, C can be enumerated4H4S、CH3C4H3S、C2H5C4H3S、
C3H7C4H3S、C4H9C4H3S、C5H11C4H3S、C6H13C4H3S、C7H15C4H3S、C8H17C4H3S、C9H19C4H3S、C10H21C4H3S、
C11H23C4H3S、C12H25C4H3S、C13H27C4H3S、C14H29C4H3S、C15H31C4H3S、C16H33C4H3S、C17H35C4H3S、
C18H37C4H3S、C3H3NS、CH3C3H2NS、C2H5C3H2NS、C3H7C3H2NS、C4H9C3H2NS、C5H11C3H2NS、C6H13C3H2NS、
C7H15C3H2NS、C8H17C3H2NS、C9H19C3H2NS、C10H21C3H2NS、C11H23C3H2NS、C12H25C3H2NS、C13H27C3H2NS、
C14H29C3H2NS、C15H31C3H2NS、C16H33C3H2NS、C17H35C3H2NS、C18H37C3H2The compounds such as NS.It should be noted that
C4H4S represents thiophene, C4H3S represents thiphene ring, C3H3NS represents thiazole, C3H2NS represents thiazole ring.
The compound represented as above-mentioned formula [12], for example, CH can be enumerated3COOCOCH3、C2H5COOCOC2H5、
C3H7COOCOC3H7、C4H9COOCOC4H9、C5H11COOCOC5H11、C6H13COOCOC6H13、C7H15COOCOC7H15、
C8H17COOCOC8H17、C9H19COOCOC9H19、C10H21COOCOC10H21、C11H23COOCOC11H23、C12H25COOCOC12H25、
C13H27COOCOC13H27、C14H29COOCOC14H29、C15H31COOCOC15H31、C16H33COOCOC16H33、C17H35COOCOC17H35、
C18H37COOCOC18H37、C6H5COOCOC6H5、CF3COOCOCF3、C2F5COOCOC2F5、C3F7COOCOC3F7、C4F9COOCOC4F9、
C5F11COOCOC5F11、C6F13COOCOC6F13、C7F15COOCOC7F15、C8F17COOCOC8F17Etc. compound.
If in addition, the compound in the compound and its salt compound that are represented selected from above-mentioned formula [6]~[12] is utilized
The HLB value that Griffin methods are obtained is 0.001~10, then higher water repellency can be assigned to metal system wafer surface, thus excellent
Choosing.
If in addition, the compound in the compound and its salt compound that are represented selected from above-mentioned formula [6]~[12] is following
Compound and its salt compound that formula [19] is represented, then can assign higher water repellency to metal system wafer surface, thus
It is preferred that.
R24-X11 [19]
[in formula [19], X11For selected from by-P (O) (OH)2、-NH2Base ,-N=C=O bases ,-SH bases ,-CONHOH bases, imidazoles
Quinoline ring group into group at least one kind of, R24It is alkyl or C that carbon number is 4~18tF2t+1-(CH2)u- base (t=4~8, u
=0~2).]
On the solvent that uses in the 2nd method of the present invention, specifically, can enumerate with described in above-mentioned 1st method
Hydro carbons, esters, ethers, ketone, the solvent containing halogens, sulfoxide series solvent, interior ester series solvent, carbonate-based solvent, no
The derivative of polyalcohol with OH bases, the same solvent of solvent of Nitrogen element without N-H bases, Yi Jishui, methanol, second
Alcohol, propyl alcohol, butanol, amylalcohol, hexanol, enanthol, octanol, ethylene glycol, diethylene glycol, 1,3- propane diols, 1,2- propane diols, a contracting two
Propane diols, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, triethylene glycol, tripropylene glycol, tetraethylene glycol, four propane diols,
The alcohols such as glycerine；Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethyl two
Alcohol monomethyl ether, TC, diethylene glycol list propyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl
Ether, triethylene glycol monoethyl ether, triethylene glycol list propyl ether, triethylene glycol monobutyl base ether, tetraethylene glycol monomethyl ether, tetrem two
Alcohol list ethylether, tetraethylene glycol list propyl ether, tetraethylene glycol single-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, third
Glycol list propyl ether, glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, a contracting two
Propylene glycol monopropyl ether, dipropylene glycol monobutyl base ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethylether, 3 the third two
Alcohol list propyl ether, tripropylene glycol monobutyl base ether, four propylene glycol monomethyl ethers, butanediol monomethyl ether etc. have the polyalcohol of OH bases
Derivative, formamide etc. have N-H bases Nitrogen element solvent.
In addition, if part or all of above-mentioned solvent uses non-flame properties material, water repellency chemical solution becomes not
Combustion property, or flash-point rise, the dangerous reduction of the chemical solution, thus preferably.Solvent containing halogens is generally noninflammability,
The non-flame properties solvent containing halogens can be suitable for use as noninflammability organic solvent.In addition, to can also act as noninflammability molten for water
Agent.
If in addition, using solvent of the flash-point more than 70 DEG C as above-mentioned solvent, coming from the viewpoint of the security in fire service law
See preferably.
In addition, according to " GHS：GHS ", flash-point is determined for less than 93 DEG C of solvent
Justice is " flammable liquid ".Therefore, even if not being noninflammability solvent, if using solvent of the flash-point more than 93 DEG C as above-mentioned solvent,
Then the flash-point of above-mentioned water repellency chemical solution is also well over 93 DEG C, because the chemical solution is difficult to meet " flammable liquid ", because
And it is further preferred from a security point of view.
In addition, the derivative of interior ester series solvent, carbonate-based solvent, polyalcohol is generally the high material of flash-point, therefore, it is possible to
The danger of above-mentioned water repellency chemical solution is reduced, thus preferably.From the viewpoint of above-mentioned security, in particular, it is preferred that
For solvent of the flash-point more than 70 DEG C or ethylene glycol, diethylene glycol, 1,2- propane diols, 1,3- third described in above-mentioned 1st method
Glycol, dipropylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, triethylene glycol, tripropylene glycol, tetrem two
Alcohol, four propane diols, glycerine, diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether, diethylene glycol
Single-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol list propyl ether, triethylene glycol monobutyl base ether,
Tetraethylene glycol monomethyl ether, tetraethylene glycol list ethylether, tetraethylene glycol list propyl ether, tetraethylene glycol single-butyl ether, a contracting dipropyl
Glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monobutyl base ether,
Tripropylene glycol monomethyl ether, tripropylene glycol list ethylether, tripropylene glycol list propyl ether, tripropylene glycol monobutyl base ether, four propane diols
Solvent of the flash-points such as monomethyl ether more than 70 DEG C, the flash-point described in more preferably above-mentioned 1st method is molten more than 93 DEG C
Agent or ethylene glycol, diethylene glycol, 1,2- propane diols, 1,3- propane diols, dipropylene glycol, 1,2- butanediols, 1,3- fourths two
Alcohol, 1,4- butanediols, triethylene glycol, tripropylene glycol, tetraethylene glycol, four propane diols, glycerine, diethylene glycol monomethyl ether, diethyl
Glycol list propyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol list third
Base ether, triethylene glycol monobutyl base ether, tetraethylene glycol monomethyl ether, tetraethylene glycol list ethylether, tetraethylene glycol list propyl ether, tetrem
Glycol single-butyl ether, dipropylene glycol list propyl ether, dipropylene glycol monobutyl base ether, tripropylene glycol monomethyl ether, 3 third
The flash-points such as glycol list ethylether, tripropylene glycol list propyl ether, tripropylene glycol monobutyl base ether, four propylene glycol monomethyl ethers are more than 93 DEG C
Solvent.
In addition, on metal system chip with it is in water repellency chemical solution, selected from what is represented by above-mentioned formula [6]~[12]
The concentration of compound and its at least one kind of compound in the group of salt compound composition, relative to the metal system chip chemical solution
The mass % of total amount 100 of liquid, preferably 0.0005~2 mass %.If less than 0.0005 mass %, assign and imitating with water repellency
Really insufficient tendency, if more than 2 mass %, with the tendency for being difficult to be dissolved in solvent.More preferably 0.001~1
Quality %, particularly preferably 0.0015~0.8 mass %.It should be noted that metal system chip water repellency chemical solution can
Using comprising lower boiling material as organic solvent, however, it is important that in the metal system chip with water repellency chemical solution
In contained composition, the boiling point of most compositions is measured by quality ratio more than 40 DEG C.More preferably above 60 DEG C of the boiling point, further
Preferably greater than 80 DEG C.
It should be noted that as solvent of the metal system chip with water repellency chemical solution, being based on imparting more excellent
Water repellency the reasons why, preferably in the derivative of hydro carbons, esters, ethers, ketone, polyalcohol do not have OH bases material, water
Or their mixed liquor.If in addition, considering the displacement property with cleaning fluid, the cleaning fluid particularly formed by water system liquid, preferably
For the derivative of the polyalcohol without OH bases, water or their mixed liquor.
In the cleaning method of the present invention, due to making above-mentioned water repellency chemical solution, i.e. silicon systems chip water repellency chemical solution
Liquid or metal system chip water repellency chemical solution are more than 40 DEG C, thus the solvent for being used to dilute in the chemical solution is preferably
The material that more than 40 DEG C of boiling point.It should be noted that boiling point can also be used to be less than 40 DEG C of solvent, but it is super to preferably use boiling point
Cross 40 DEG C of other solvents as measured by quality ratio in composition contained in the water repellency chemical solution most composition (with
Under, main solvent composition is designated as sometimes).Above-mentioned main solvent composition more preferably boiling point is more than 50 DEG C of material, further especially excellent
Elect more than 70 DEG C of material as.
In addition, except the silicon compound A, acid or alkali, solvent of above-mentioned formula [1] expression, above-mentioned silicon systems chip water repellency
Chemical solution can also contain additive etc..In addition, similarly, except selected from the chemical combination represented by above-mentioned formula [6]~[12]
Beyond at least one kind of compound and solvent in the group of thing and its salt compound composition, above-mentioned metal system chip water repellency chemistry
Solution can also contain additive etc..As the additive, the oxidants such as hydrogen peroxide, ozone, surfactant can be enumerated
Deng.In addition, there is above-mentioned silicon compound A in a part for the relief pattern of chip or represented with above-mentioned formula [6]~[12]
Compound can not form the material of water repellency overlay film in the case of, can be added in the material can form water repellency overlay film
Material.In addition, for the purpose obtained beyond silicon compound B, may be used also with water repellency chemical solution in above-mentioned silicon systems chip
To add other acid.
In the present invention, as long as above-mentioned water repellency chemical solution can be kept or clear at least recess of the relief pattern of chip
Washing lotion, then the cleaning way of the chip is not particularly limited.As the cleaning way of chip, following manner can be enumerated：With
Rotary-cleaning is individual mode of representative, wherein, chip is nearly horizontally kept on one side and it is rotated, while liquid is supplied
Clean near to pivot and one by one chip；Chip more than two panels and the interval side cleaned are impregnated in rinse bath
Formula.It should be noted that supplying above-mentioned water repellency chemical solution or cleaning fluid as at least recess of the relief pattern to chip
When the water repellency chemical solution or cleaning fluid form, as long as being not particularly limited when being held in the recess for liquid, example
If any liquid, steam etc..
In the present invention, as long as chip is not particularly limited with relief pattern, for example, using the recess in relief pattern
Surface include the chip of element silicon；Or the chip with least one kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and ruthenium.
For example also include at least recess surface shape of chip in chip of the surface comprising element silicon of the recess of relief pattern
Into the chip of at least one kind of composition in silicon, silica and silicon nitride；Or when forming relief pattern, at least recess
Surface is the chip of at least one kind of composition in silicon, silica and silicon nitride.Alternatively, it is also possible to at least recessed of chip
The part on portion surface forms the chip of at least one kind of composition in silicon, silica and silicon nitride；Or it is concavo-convex being formed
During pattern, at least a part for recess surface is the chip of at least one kind of composition in silicon, silica and silicon nitride.The feelings
Under condition, selected from least one kind of surface being present at least silicon of a part for recess surface, silica and silicon nitride, lead to
Cross silicon systems chip water repellency chemical solution formation water repellency overlay film.Therefore, above-mentioned water repellency overlay film can also be present in above-mentioned
A part at least recess surface of chip.
In addition, having at least one kind of element in titanium, tungsten, aluminium, copper, tin, tantalum and ruthenium on the surface of the recess of relief pattern
Chip can be enumerated by silicon wafer, by comprising silicon and/or silica (SiO2) two or more compositions formation chip, carbon
Surface titanium, titanium nitride, the dioxy of SiClx chip, sapphire wafer, various compound semiconductor wafers and plastic substrate etc.
Change material, aluminium, the aluminum oxide comprising wolfram element such as the material comprising titanium elements such as titanium or tungsten, tungsten oxide etc. and include aluminium element
Material, tin, the tin oxide comprising copper such as material, copper, cupric oxide etc. include material, tantalum nitride, the tantalum oxide of tin element
Deng the coated chip of the layer of the materials comprising ruthenium element such as material or ruthenium, ruthenium-oxide comprising tantalum element；Or in crystalline substance
Multilayer film is formed on piece, at least 1 layer therein is chip of layer of material comprising above-mentioned metal series elements etc., above-mentioned bumps
Pattern formation process is carried out in the layer of the layer comprising the material containing above-mentioned metal series elements.It is additionally comprised in form bump maps
At least a portion on the surface of the relief pattern is the crystalline substance with the material of at least one kind of element in above-mentioned metal series elements during case
Piece.
In addition, even for by comprising with above-mentioned metal series elements the material of at least one kind of element it is two or more
The chip that composition is constituted, also can be using above-mentioned metal system chip water repellency chemical solution in above-mentioned metal series elements
The surface of the material of at least one kind of element forms water repellency overlay film.As the chip that this is made up of two or more compositions, in addition to
The chip with the material of at least one kind of element in metal series elements is formed in a part at least recess surface；Or formed
During relief pattern, at least a part for recess surface is the chip with the material of at least one kind of element in metal series elements.Need
Illustrate, can be above-mentioned bumps using the metal system chip water repellency chemical solution formation water repellency overlay film of the present invention
Surface in pattern, with the material part of at least one kind of element in metal series elements.Therefore, above-mentioned water repellency overlay film can be with
A part using metal system chip with water repellency chemical solution at least recess surface of above-mentioned metal system chip is formed.
In addition, the cleaning method of the present invention particularly preferably has following process.
(process 1) makes wafer surface behind the face with relief pattern, water system liquid to be supplied into the face, in relief pattern
At least recess keep water system liquid process；
(process 2) is held in recessed with the boiling point comprising more than 80 mass % for the cleaning fluid displacement of 55~200 DEG C of solvent
The process of the liquid of at least recess of convex pattern；
(process 3) replaces above-mentioned cleaning fluid with water repellency chemical solution, and the chemical solution is held in into relief pattern extremely
The process of few recess；
(process 4) is by drying the process that liquid is removed from relief pattern surface；
The process that (process 5) removes water repellency overlay film.
First, as described above described in (process 1), water system liquid is made to be held at least recess of relief pattern.It is used as mixing
To the acid in above-mentioned water system liquid, there are inorganic acid, organic acid.As the example of inorganic acid, hydrofluoric acid, buffering hydrogen fluorine can be enumerated
Acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid etc., as the example of organic acid, can enumerate methanesulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, three
Fluorine methanesulfonic acid, acetic acid, trifluoroacetic acid, five fluorine propionic acid etc..As the alkali being mixed into the cleaning fluid, ammonia, choline etc. can be enumerated.
As the oxidant being mixed into the cleaning fluid, ozone, hydrogen peroxide etc. can be enumerated.
Then, it is 55~200 DEG C of solvent with the boiling point comprising more than 80 mass % as described above described in (process 2)
Cleaning fluid replaces the liquid for being held in recess.It should be noted that the liquid that recess is held in before displacement can be above-mentioned water system
Liquid or flushing liquor A described later.
Above-mentioned cleaning fluid is preferably selected from being mixed with organic solvent, acid, alkali, oxidant by organic solvent, water, in water
At least one kind of aqueous solution composition group at least one kind of liquid.
It should be noted that in the case of the above-mentioned cleaning fluid for preparing the organic solvent comprising boiling point less than 55 DEG C, will
Organic solvent of the boiling point less than 55 DEG C is mixed with water, boiling point for 55~200 DEG C of organic solvent, includes resulting mixed liquor
More than 80 mass % boiling point is 55~200 DEG C of solvent, prepares above-mentioned cleaning fluid.In addition, preparing comprising boiling point more than 200
DEG C organic solvent above-mentioned cleaning fluid in the case of, be 55~200 by organic solvent of the boiling point more than 200 DEG C and water, boiling point
DEG C organic solvent mixing, it is 55~200 DEG C of solvent to make boiling point of the resulting mixed liquor comprising more than 80 mass %, is prepared
Above-mentioned cleaning fluid.
It should be noted that from the viewpoint of cleanliness factor, above-mentioned cleaning fluid be preferably organic solvent, water, water with it is organic
The mixed liquor of solvent.If in addition, the cleaning fluid be organic solvent, can make above-mentioned water repellency chemical solution do not contacted with water and
Recess is supplied to, thus preferably.Particularly, if the organic solvent is (molten in 100 mass parts water comprising water-miscible organic solvent
Xie Du is more than 5 mass parts), then easily by water system liquid displacement, thus preferably.
It should be noted that the bumps can also will be held in after the process (process 1) that recess keeps water system liquid
The above-mentioned water system liquid displacement of at least recess of pattern is into the liquid (be sometimes below designated as flushing liquor A) different from the liquid
Afterwards, it is transferred to the process (process 2) replaced with above-mentioned cleaning fluid.
It should be noted that as above-mentioned flushing liquor A, two or more liquid can be replaced and used.For example, being used as punching
Washing lotion A, can be replaced into after water, and then is replaced into organic solvent (preferably comprising water-miscible organic solvent) and uses.
Then, (process 3) is described as described above, above-mentioned water repellency chemical solution is held at least recess of relief pattern,
Above-mentioned water repellency overlay film is formed in the recess surface of the relief pattern of chip by water repellency chemical solution.The process of above-mentioned displacement
The temperature of the water repellency chemical solution of middle supply is 40 DEG C of boiling points less than the water repellency chemical solution.
When the recess surface of the relief pattern of chip is formed with above-mentioned water repellency overlay film by water repellency chemical solution, if
It is assumed that the contact angle when surface maintains water is 50~130 °, then it is not susceptible to pattern and topples over, thus preferably.In addition, contact
Angle is closer to 90 °, then the capillary force for acting on the recess is smaller, is less susceptible to generation pattern and topples over, therefore particularly preferably 60~
120 °, more preferably 70~110 °.In addition, capillary force is preferably 2.1MN/m2Below.If the capillary force is 2.1MN/m2With
Under, then it is not susceptible to pattern and topples over, thus preferably.If in addition, the capillary force diminishes, being less susceptible to generation pattern and toppling over, thus
The capillary force is particularly preferably 1.5MN/m2Below, it is more preferably 1.0MN/m2Below.It is furthermore desirable that will be with liquid
Contact angle adjust near 90 ° so that capillary force is ad infinitum close to 0.0MN/m2。
Then, (process 4) is described as described above, carries out by drying the process that liquid is removed from relief pattern surface.The work
In sequence, the liquid on relief pattern surface is held in by drying removal.The drying preferably passes through spin drying method, IPA (2- third
Alcohol) steam drying, Marangoni dry (Marangoni drying), heat drying, forced air drying, heated-air drying, vacuum do
Drying means known to dry grade is carried out.
It should be noted that can also at least recess that water repellency chemical solution is held in relief pattern process
After (process 3), will be held at least recess of the relief pattern water repellency chemical solution be replaced as it is different from the chemical solution
Liquid (being designated as flushing liquor B sometimes below) after, be transferred to by dry from relief pattern surface remove liquid process (work
Sequence 4).
In addition, as above-mentioned flushing liquor B, two or more cleaning fluids can be replaced and used.For example, as flushing liquor B,
It can be replaced into after organic solvent (preferably comprising water-miscible organic solvent), and then be replaced into water system liquid and use.
As above-mentioned flushing liquor A and flushing liquor B example, the mixing of water, organic solvent, water and organic solvent can be enumerated
Thing, at least one kind of material being mixed with them in acid, alkali, surfactant or in them with less than above-mentioned water repellency
The mode of the concentration of in chemical solution, following added compounds with the addition of being selected from for above-mentioned water repellency chemical solution
By above-mentioned silicon compound A, silicon compound the A compound represented with acid or alkali and above-mentioned formula [6]~[12] and its salt compound
The material of at least one kind of compound in the group of composition.
It should be noted that the organic solvent of one of preference as above-mentioned cleaning fluid, flushing liquor A and flushing liquor B
Example, can enumerate hydro carbons, esters, ethers, ketone, the solvent containing halogens, sulfoxide series solvent, alcohols, polyalcohol and spread out
Biology, solvent of Nitrogen element etc..
As the concrete example of above-mentioned organic solvent, can enumerate is used to dilute in silicon systems chip water repellency chemical solution
Organic solvent, with the metal system chip organic solvent same with the organic solvent used in water repellency chemical solution.
When removing liquid from above-mentioned relief pattern surface, the liquid for being held in the surface can be above-mentioned water repellency chemical solution
Liquid, flushing liquor B and their mixed liquor.It should be noted that the mixed liquor comprising above-mentioned water repellency chemical solution can be by
Above-mentioned water repellency chemical solution is replaced into the liquid of the state in flushing liquor B way or in advance by above-mentioned water repellency
Learn the mixed liquor obtained by solution is mixed into the flushing liquor B different from the water repellency chemical solution.Furthermore it is possible to temporary in liquid
When be removed from above-mentioned relief pattern surface after, flushing liquor B or above-mentioned mixed liquor is held in above-mentioned relief pattern surface, it
After be dried.When liquid is removed from above-mentioned relief pattern surface, water repellency overlay film is present in the surface of the recess, thus applies
It is added to the capillary force reduction of the recess, it is difficult to occur pattern and topple over.
It should be noted that in by the dry process (process 4) for removing liquid from relief pattern surface, from bump maps
When the removed liquid in case surface is water in above-mentioned flushing liquor B, above-mentioned organic solvent or their mixture, dirt after drying
It is difficult to residue in wafer surface, thus preferably.If in addition, water system liquid, particularly water, then pass through above-mentioned water repellency chemical solution
Liquid carries out the recess surface of the relief pattern of water repellent and becomes big with the contact angle θ of the liquid, and the capillary force P for acting on the recess becomes
It is small, thus preferably.
It should be noted that on above-mentioned cleaning fluid, flushing liquor A and flushing liquor B, can be with 10 DEG C less than the liquid
Boiling point temperature keep.For example, as above-mentioned flushing liquor A, using the solution comprising acidic aqueous solution, particularly preferably using bag
Containing acidic aqueous solution and solution of the boiling point for more than 100 DEG C of organic solvent, if making flushing liquor A temperature bring up to the flushing liquor
Near A boiling point, above-mentioned water repellency overlay film is easily formed with the short time, thus preferably.
Then, (process 5) is described as described above, the process for being removed water repellency overlay film.Removing above-mentioned water repellency overlay film
When, C-C keys, the C-F keys cut off in the water repellency overlay film is effective.As its method, do not have then as long as above-mentioned key can be cut off
Be particularly limited to, for example, can enumerate to wafer surface carry out light irradiation, chip is heated, to chip progress ozone it is sudden and violent
Reveal, plasma irradiating is carried out to wafer surface, corona discharge etc. is carried out to wafer surface.
In the case of removing above-mentioned water repellency overlay film with light irradiation, preferably irradiation is comprising in energy and the water repellency overlay film
C-C keys, C-F keys bond energy 83kcal/mol, 116kcal/mol it is suitable, wavelength be less than 340nm, 240nm ultraviolet.Make
For the light source, metal halide lamp, low pressure mercury lamp, high-pressure sodium lamp, Excimer lamp, carbon arc etc. can be used.Shone on ultraviolet
Intensity is penetrated, if metal halide lamp, for example, with photometer (Konica Minolta Sensing, Inc., the irradiation of manufacture
Intensitometer UM-10, light receiver UM-360 (peak sensitivity wavelengths：365nm, measure wave-length coverage：310~400nm)) measure
Value meter is preferably 100mW/cm2Above, particularly preferably 200mW/cm2More than.It should be noted that exposure intensity is less than
100mW/cm2When, removing above-mentioned water repellency overlay film needs for a long time.If in addition, low pressure mercury lamp, then the shorter purple of illumination wavelength
Outside line, even if thus exposure intensity is low, above-mentioned water repellency overlay film can be also removed with the short time, thus preferably.
In addition, in the case of removing above-mentioned water repellency overlay film with light irradiation, if utilizing the above-mentioned water repellency of ultraviolet light degradation
Ozone is produced while the constituent of overlay film, and makes by the ozone constituent voloxidation of above-mentioned water repellency overlay film,
Then processing time can shorten, thus particularly preferably.As the light source, low pressure mercury lamp, Excimer lamp can be used.In addition, also may be used
To be heated when carrying out light irradiation to chip.
In the case where being heated to chip, with the heating of 400~700 DEG C, preferably 500~700 DEG C progress chips.
Preferably, the heat time is kept for 0.5~60 minute, is preferably kept for 1~30 minute and carried out.Alternatively, it is also possible in the work
Ozone exposure, plasma irradiating, corona discharge etc. are shared in sequence.Alternatively, it is also possible to carry out light irradiation when heating chip.
In the case of carrying out ozone exposure to chip, preferably by the ultraviolet irradiation using low pressure mercury lamp etc., high electricity is utilized
Low temperature discharge of pressure etc. and the ozone supply that produces are to wafer surface.Illumination can also be carried out when carrying out ozone exposure to chip
Penetrate, can also be heated.
In the process of the water repellency overlay film of above-mentioned removal wafer surface, by the way that above-mentioned light irradiation, heating, ozone is sudden and violent
Dew, plasma irradiating, corona discharge etc. are combined, and can effectively remove the water repellency overlay film of wafer surface.
Embodiment
On the surface of chip is made into the face with relief pattern, various researchs were carried out in other documents etc.,
It is established technology, therefore with the evaluation of the surface treatment of the chip that has used above-mentioned water repellency chemical solution in the present invention
Centered on and carry out.In addition, can be clear and definite by following formula, pattern topples over largely dependent on kept liquid and chip table
The contact angle of the drop of the contact angle in face, the i.e. liquid and the surface tension of the liquid.
P=2 × γ × cos θ/S
(in formula, γ is the surface tension for the liquid for being held in recess, and θ is recess surface and the liquid institute for being held in recess
Into contact angle, S be recess width).In the case of liquid being maintained in the recess 4 of relief pattern 2, the drop of the liquid
Contact angle has correlation with acting on the capillary force (being toppled over it is believed that being equivalent to pattern) of the recess, thus can be according to above formula
Evaluation with the contact angle of the drop of water repellency overlay film 12 exports capillary force.It should be noted that in embodiment, as upper
Liquid is stated, the water for the representative substances for belonging to water system liquid is used.
But, in the case of there is the chip of relief pattern on surface, it is impossible to correctly evaluate and be formed at the relief pattern
The above-mentioned contact angle of itself of water repellency overlay film 12 on surface.
On the evaluation of the contact angle of water droplet, remember in such as JIS R 3257 " base plate glass wettability of the surface test method "
As load, number μ l water droplet is added dropwise on sample (base material) surface, is entered by determining water droplet and substrate surface angulation
OK.But, in the case of having figuratum chip, contact angle can become very large.This be due to produce Wenzel effects,
Cassie effects, cause contact angle by the influence of the surface configuration (roughness, roughness) of base material, and make on apparent
The reason of the contact angle increase of water droplet.
Therefore, the chip that above-mentioned water repellency chemical solution is smooth for surface is formed in wafer surface in the present embodiment
Water repellency overlay film, and the water repellency that the surface that the water repellency overlay film is considered as the chip 1 that relief pattern 2 is formed with surface is formed
Overlay film 12, so as to carry out various evaluations.It should be noted that in the present embodiment, as the smooth silicon systems chip in surface, using
On the smooth silicon wafer in surface " chip with heat oxide film " with smooth thermal oxide film layer, in the smooth silicon in surface
Have on chip " chip with silicon nitride film " of smooth silicon nitride layer.In addition, as the smooth metal system chip in surface, making
With on the smooth silicon wafer in surface with titanium nitride layer " chip with titanium nitride film ", on the smooth silicon wafer in surface
" chip with tungsten film " and on the smooth silicon wafer in surface " chip with ruthenium film " with layer of ruthenium with tungsten layer.
When rotating chip in cleaning method by liquid for chip, be extremely hard to closely to reproduce from cleaning fluid to
The state of water repellency chemical solution displacement, therefore, in the present embodiment, by the chip that will be impregnated in cleaning fluid with the chip table
The state that face maintains above-mentioned cleaning fluid is impregnated into water repellency chemical solution, so as to reproduce displacement shape with good precision
State.In addition, by carrying out various changes to the time impregnated in above-mentioned water repellency chemical solution, have rated and change entering for displacement
Chip when stroke is spent refuses hydrated state (state of water repellency overlay film).
Detailed content is as follows.Evaluation method, water repellent of the chip described below for having supplied water repellency chemical solution
The preparation of property chemical solution and supply the evaluation result after the water repellency chemical solution to chip.
(evaluation method for having supplied the chip of water repellency chemical solution)
As the evaluation method for the chip for having supplied water repellency chemical solution, the evaluation of following (1)~(2) has been carried out.
(1) it is formed at the contact angle evaluation of the water repellency overlay film of wafer surface
The placement μ l of pure water about 2 in the wafer surface of water repellency overlay film are being formed with, (consonance interface science is public with contact angle meter
Department's system：CA-X types) determine water droplet and angle (contact angle) formed by wafer surface.This measure is carried out at the 5 of above-mentioned wafer surface,
Calculate average value.
(2) evaluation of capillary force
P is calculated using following formula, capillary force (P absolute value) is obtained.
P=2 × γ × cos θ/S
(in formula, γ is the surface tension for the liquid for being held in recess, and θ is recess surface and the liquid institute for being held in recess
Into contact angle, S be recess width.)
It should be noted that in the present embodiment, being used as one of pattern form, it has been assumed that line width (width of recess) is
The chip of 45nm line and the pattern of spacing shape.Recess width for 45nm pattern in, gas-liquid interface passes through bump maps
In the case that cleaning fluid during case is water, pattern has the tendency easily toppled over, and cleaning fluid is in the case of 2- propyl alcohol, pattern has
Have the tendency of to be difficult to topple over.It is that in the case that 45nm, wafer surface are silica, cleaning fluid is 2- propyl alcohol in the width of recess
(surface tension：22mN/m, the contact angle for silicon oxide surface：1 °) when, capillary force is 0.98MN/m2.On the other hand, except
Maximum water (the surface tension of surface tension in liquid outside mercury：72mN/m, the contact angle with silica：2.5 °) in capillary force
For 3.2MN/m2.In addition, in the case where wafer surface is such as titanium nitride, tungsten, ruthenium, 2- propyl alcohol is equal to the contact angle on the surface
For 0.5 °, similarly water is 2 ° to the contact angle on the surface.In addition, in other things for including titanium elements, wolfram element, ruthenium element
Also it is same degree in matter (for example, titanium, titanium dioxide, tungsten oxide, ruthenium-oxide etc.).Nitrogenized in the width of recess for 45nm band
In the case of the chip of titanium film, the chip with tungsten film, the chip with ruthenium film, cleaning fluid is 2- propyl alcohol (surface tension：22mN/m)
When, capillary force is 0.98MN/m2.On the other hand, the maximum water (surface tension of surface tension in the liquid in addition to mercury：
Capillary force is 3.2MN/m in 72mN/m)2。
[embodiment 1-1]
(1) chip is cleaned using cleaning fluid
By the smooth chip (surface has the silicon systems chip for the thermal oxide film layer that thickness is 1 μm) with heat oxide film in room
It is impregnated in 1 mass % hydrofluoric acid aqueous solution 2 minutes, is then impregnated 1 minute in pure water, in 2- propyl alcohol (iPA under temperature；Boiling
Point 82 DEG C) in dipping 1 minute.Therefore, the cleaning fluid that the wafer surface is kept after cleaning is iPA.
(2) preparation of water repellency chemical solution
In the present embodiment, silicon compound A HMDS ((H will be used as3C)3Si-NH-Si(CH3)3) 5g, work
For silicon compound B trimethyl silyl trifluoro-acetate ((CH3)3Si-OC(O)CF3) 0.1g and as organic solvent third
Glycol monomethyl ether acetic acid esters (PGMEA) 94.9g is mixed, and obtains water repellency chemical solution.It should be noted that in the water repellency
Most compositions are measured in chemical solution in contained composition by quality ratio for PGMEA, its boiling point is 146 DEG C.
(3) cleaning fluid of wafer surface is replaced using water repellency chemical solution
The water repellency chemical solution prepared in above-mentioned " preparation of (2) water repellency chemical solution " is heated to 40 DEG C, will be upper
State the chip with heat oxide film prepared in " cleaning of (1) chip " impregnated in the chemical solution the various times (5,10,20,
30th, 40,50,60 seconds), cleaning fluid is replaced, water repellency overlay film is formed.Afterwards, by the chip with heat oxide film from the chemical solution
Lift, as flushing liquor, impregnate 60 seconds, then impregnated 60 seconds in pure water in iPA.
(4) drying of chip
Finally, the chip with heat oxide film is taken out from pure water, injection air carries out forced air drying, by the pure water on surface
Remove.
Obtained by being evaluated using the main points described in above-mentioned " evaluation method for having supplied the chip of water repellency chemical solution "
The chip with heat oxide film, investigation in order that surface treatment after the chip with heat oxide film contact angle for more than 75 °,
More than 80 ° and more than 85 ° (that is, capillary force is respectively 0.8MN/m2Below, 0.6MN/m2Below and 0.3MN/m2Required for below)
The surface treatment time (time swap).Show the result in table 1.
[table 1]
[embodiment 1-2~1-10, comparative example 1-1~1-5]
The temperature of the water repellency chemical solution used in change embodiment 1-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with heat oxide film is carried out, and then carries out its evaluation.Show the result in table 1.Need
Illustrate, DEGEEA refers to TC acetic acid esters, the institute in the water repellency chemical solution for used the solvent
Among the composition contained, most compositions are measured by quality ratio for DEGEEA, and its boiling point is 218 DEG C.In addition, PGDA refers to propane diols
Diacetate esters, in the water repellency chemical solution for used the solvent among contained composition, measure by quality ratio it is most into
It is divided into PGDA, its boiling point is 190 DEG C.In addition, PGMEA/DEE refers to PGMEA and diethyl ether (DEE；35 DEG C of boiling point) with 90:10
The solvent that mixes of mass ratio, in the water repellency chemical solution for used the mixed solvent among contained composition, with
It is PGMEA that mass ratio, which measures most compositions, and its boiling point is 146 DEG C.Similarly, PGMEA/DEGEEA refer to PGMEA and
DEGEEA is with 90:The solvent that 10 mass ratio is mixed, it is contained in the water repellency chemical solution for used the mixed solvent
Composition among, most compositions are measured by quality ratio for PGMEA, its boiling point is 146 DEG C.Similarly, DEGEEA/PGMEA is
Refer to DEGEEA and PGMEA with 90:The solvent that 10 mass ratio is mixed, the institute in the cleaning fluid for used the mixed solvent
Among the composition contained, most compositions are measured by quality ratio for DEGEEA, and its boiling point is 218 DEG C.
[embodiment 2-1]
Silicon compound D HMDS ((H will be used as3C)3Si-NH-Si(CH3)3) 5g, the trifluoro as sour D
Acetic anhydride ({ CF3C(O)}2O) 0.1g and as organic solvent PGMEA 94.9g mix, react it, thus obtain comprising make
For silicon compound B trimethyl silyl trifluoro-acetate, the HMDS as silicon compound A, as organic
The PGMEA of solvent water repellency chemical solution is in addition, identical with embodiment 1-1.It should be noted that in the water repellency
In chemical solution among contained composition, most compositions are measured by quality ratio for PGMEA, and its boiling point is 146 DEG C.The present embodiment
Water repellency chemical solution in contained HMDS be not consumed in above-mentioned silicon compound B reaction for obtaining
Silicon compound D, the composition plays silicon compound A function.Show the result in table 2.
[table 2]
[embodiment 2-2~2-6, comparative example 2-1~2-4]
The temperature of the water repellency chemical solution used in change embodiment 2-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with heat oxide film is carried out, and then carries out its evaluation.Show the result in table 2.
[embodiment 3-1]
Except sour D is changed into trifluoroacetic acid (CF3C (O)-OH) beyond, it is identical with embodiment 2-1.It should be noted that
In the water repellency chemical solution obtained in the present embodiment among contained composition, most compositions are measured by quality ratio is
PGMEA, its boiling point is 146 DEG C.Show the result in table 3.
[table 3]
[embodiment 3-2~3-6, comparative example 3-1~3-4]
The temperature of the water repellency chemical solution used in change embodiment 3-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with heat oxide film is carried out, and then carries out its evaluation.Show the result in table 3.
[embodiment 4-1]
Use trimethyl silyl dimethyl amine ((CH3)3Si-N(CH3)2) as silicon compound A, closed without using silication
Thing B is in addition, identical with embodiment 1-1.It should be noted that in the water repellency chemical solution obtained in the present embodiment
Among contained composition, most compositions are measured by quality ratio for PGMEA, and its boiling point is 146 DEG C.Show the result in table 4.
[table 4]
[embodiment 4-2~4-4, comparative example 4-1~4-2]
The temperature of the water repellency chemical solution used in change embodiment 4-1, the cleaning fluid of water repellent before processing, carry out band heat
The surface treatment of the chip of oxide-film, and then carry out its evaluation.Show the result in table 4.
[embodiment 5-1]
Use octyldimethyl (dimethylamino) silane (C8H17Si(CH3)2-N(CH3)2) as silicon compound A, except this
In addition, it is identical with embodiment 4-1.It should be noted that in the water repellency chemical solution obtained in the present embodiment it is contained into
/ in, most compositions are measured by quality ratio for PGMEA, and its boiling point is 146 DEG C.Show the result in table 5.
[table 5]
[embodiment 5-2~5-7, comparative example 5-1~5-2]
The temperature of the water repellency chemical solution used in change embodiment 5-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with heat oxide film is carried out, and then carries out its evaluation.Show the result in table 5.Need
Illustrate, DPGMEA refers to dipropylene glycol monomethyl ether acetate (boiling point：213 DEG C), 13BGDA refers to 1,3- fourths two
Alcohol diacetate esters (boiling point：232℃).
[embodiment 6-1]
(1) chip is cleaned using cleaning fluid
By the smooth chip (surface has the silicon systems chip for the silicon nitride layer that thickness is 50nm) with silicon nitride film in room
It is impregnated in 1 mass % hydrofluoric acid aqueous solution 2 minutes, is then impregnated 1 minute in pure water at room temperature, in 28 matter under temperature
Measure % ammoniacal liquor:30 mass % hydrogenperoxide steam generators:Water is 1:1:Impregnated 1 minute in 70 DEG C in the mixed liquor of 5 (volume ratios), in room
Impregnate 1 minute, impregnated 1 minute in iPA, in PGMEA (boiling points in pure water under temperature：146 DEG C) in dipping 1 minute.Therefore, clearly
The cleaning fluid that the wafer surface is kept after washing is PGMEA.
(2) preparation of water repellency chemical solution
Silicon compound D octyldimethyl (dimethylamino) silane (C will be used as8H17Si(CH3)2-N(CH3)2) 5g, work
For sour D TFAA ({ CF3C(O)}2O) 0.2g and as organic solvent PGMEA 94.8g mix, react it, from
And obtain including the octyldimethyl silicyl trifluoro-acetate as silicon compound B, the octyl group diformazan as silicon compound A
Base (dimethylamino) silane, as organic solvent PGMEA water repellency chemical solution.It should be noted that in the water repellent
Property chemical solution among contained composition, most compositions are measured by quality ratio for PGMEA, its boiling point is 146 DEG C.
Using the method same with embodiment 1-2, the wafer surface with silicon nitride film is handled with water repellency chemical solution, and
Evaluated.Show the result in table 6.
[table 6]
[embodiment 6-2~6-6, comparative example 6-1~6-2]
The temperature of the water repellency chemical solution used in change embodiment 6-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with silicon nitride film is carried out, and then carries out its evaluation.Show the result in table 6.Need
Illustrate, PGMEA/GBL refers to PGMEA:Gamma-butyrolacton=60:The mixed solvent of 40 (mass ratioes).In addition, using
In the water repellency chemical solution of the mixed solvent among contained composition, most compositions are measured by quality ratio for PGMEA, it boils
Point is 146 DEG C.
[embodiment 7-1]
(1) chip is cleaned using cleaning fluid
By the smooth chip (surface has the silicon wafer for the titanium nitride layer that thickness is 50nm) with titanium nitride film in room temperature
Under be impregnated in 1 mass % hydrogenperoxide steam generator 1 minute, then impregnated 1 minute in pure water at room temperature, in PGMEA (boilings
Point：146 DEG C) in dipping 1 minute.Therefore, the cleaning fluid that the wafer surface is kept after cleaning is PGMEA.
(2) preparation of water repellency chemical solution
By perfluoro hexyl ethylphosphonic acid (C6F13-C2H4-P(O)(OH)2) 0.01g and the PGMEA as solvent:IPA=
99.89:The mixed solvent 99.99g mixing of 0.1 (mass ratio), stirs 18 hours and obtains water repellency chemical solution.Need explanation
, in the water repellency chemical solution among contained composition, most compositions are measured by quality ratio for PGMEA, its boiling point
For 146 DEG C.
Using the method same with embodiment 1-2, the wafer surface with titanium nitride film is handled with water repellency chemical solution, and
Evaluated.Show the result in table 7.
[table 7]
[embodiment 7-2~7-5, comparative example 7-1~7-2]
The temperature of the water repellency chemical solution used in change embodiment 7-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with titanium nitride film is carried out, and then carries out its evaluation.Show the result in table 7.Need
Illustrate, DEGEEA/iPA refers to DEGEEA:IPA=99.89:The mixed solvent of 0.1 (mass ratio), is using the mixing
In the water repellency chemical solution of solvent among contained composition, most compositions are measured by quality ratio for DEGEEA, its boiling point is
218℃.In addition, PGDA/iPA refers to PGDA:IPA=99.89:The mixed solvent of 0.1 (mass ratio), having used, the mixing is molten
In the water repellency chemical solution of agent among contained composition, most compositions are measured by quality ratio for PGDA, and its boiling point is 190
℃.In addition, DPGMEA/iPA refers to DPGMEA:IPA=99.89:The mixed solvent of 0.1 (mass ratio), is using the mixing
In the water repellency chemical solution of solvent among contained composition, most compositions are measured by quality ratio for DPGMEA, its boiling point is
213℃.In addition, 13BGDA/iPA refers to 13BGDA:IPA=99.89:The mixed solvent of 0.1 (mass ratio), is mixed having used this
In the water repellency chemical solution of bonding solvent among contained composition, most compositions are measured by quality ratio for 13BGDA, its boiling point
For 232 DEG C.
[embodiment 8-1]
By octyl phosphonic acid (C8H17-P(O)(OH)2) 0.01g and the PGMEA as solvent:IPA=99.89:0.1 (quality
Than) mixed solvent 99.99g mixing, stirring 18 hours and obtain water repellency chemical solution, in addition, with embodiment 7-1 phases
Together.It should be noted that among composition contained in the water repellency chemical solution obtained in the present embodiment, measuring by quality ratio
Most compositions is PGMEA, and its boiling point is 146 DEG C.Show the result in table 8.
[table 8]
[embodiment 8-2~8-4, comparative example 8-1~8-2]
The temperature of the water repellency chemical solution used in change embodiment 8-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with titanium nitride film is carried out, and then carries out its evaluation.Show the result in table 8.
[embodiment 9-1]
Chip uses the smooth chip (surface has the silicon wafer for the tungsten layer that thickness is 50nm) with tungsten film, at room temperature
It is impregnated in 5 mass % ammoniacal liquor 1 minute, is then impregnated 1 minute in pure water at room temperature, in PGMEA (boiling points：146℃)
Middle dipping is surface-treated after 1 minute, in addition, identical with embodiment 7-1.Therefore, the wafer surface is kept after cleaning
Cleaning fluid be PGMEA.Show the result in table 9.
[table 9]
[embodiment 9-2~9-4, comparative example 9-1~9-3]
The temperature of the water repellency chemical solution used in change embodiment 9-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of solution is learned, the surface treatment of the chip with tungsten film is carried out, and then carries out its evaluation.Show the result in table 9.
[embodiment 10-1]
Chip is using the smooth chip (surface has the silicon wafer for the layer of ruthenium that thickness is 300nm) with ruthenium film, in room temperature
Under be impregnated in 5 mass % ammoniacal liquor 1 minute, then impregnated 1 minute in pure water at room temperature, in PGMEA (boiling points：146
DEG C) in dipping 1 minute after, be surface-treated, it is in addition, identical with embodiment 7-1.Therefore, wafer surface after cleaning
The cleaning fluid of holding is PGMEA.Show the result in table 10.
[table 10]
[embodiment 10-2~10-5, comparative example 10-1~10-3]
The temperature of the water repellency chemical solution used in change embodiment 10-1, the cleaning fluid of water repellent before processing, water repellency
The solvent of chemical solution, carries out the surface treatment of the chip with ruthenium film, and then carries out its evaluation.Show the result in table 10.
In embodiment, the boiling point for making the cleaning fluid of water repellent before processing is 55~200 DEG C, makes the temperature of water repellency chemical solution
For 40 DEG C of boiling points less than the water repellency chemical solution, in the present embodiment, water repellent can be assigned with the short time by confirming
Property.On the other hand, in comparative example, confirming the imparting of water repellency needs the time.Therefore, in comparative example, even in from cleaning fluid
Made annealing treatment after to the replacement completion of chemical solution, improve chemical solution temperature, promote the formation of water repellency overlay film, displacement
The required time is also long, and the additional time is needed for the heating of chemical solution, therefore can not be as the embodiment with short-term
Between assign water repellency., can be with if can confirm that the temperature for further improving water repellency chemical solution in addition, in embodiment
The shorter time assigns water repellency.
Description of reference numerals
1 chip
The relief pattern of 2 wafer surfaces
The convex portion of 3 patterns
The recess of 4 patterns
The width of 5 recesses
The height of 6 convex portions
The width of 7 convex portions
8 cleaning fluids
9 water repellency chemical solutions
10 cleaning fluids and the situation of water repellency chemical solution mixing
The situation of 11 cleaning fluids evaporation
12 water repellency overlay films
Claims (9)
1. a kind of cleaning method of chip, it is characterised in that it is the cleaning method for the chip that surface has relief pattern, and it is extremely
There is following process less：
The process that the chip is cleaned with cleaning fluid；
The process that the cleaning fluid for the recess for being held in chip after cleaning is replaced with water repellency chemical solution；
The process for drying chip,
Boiling point of the cleaning fluid comprising more than 80 mass % is 55~200 DEG C of solvent,
The temperature of the water repellency chemical solution supplied in process by making the displacement is 40 DEG C less than the water repellency
The boiling point of chemical solution, so that at least make the recess surface water repellent,
The chip is that the chip of element silicon is included on the surface of recess, and the water repellency chemical solution includes following formulas [1]
The silicon compound A of expression, or comprising silicon compound A and acid or alkali,
The water repellency chemical solution be only by hydro carbons, esters, ethers, ketone, the solvent containing halogens, sulfoxide series solvent,
The solvent or their mixed liquor of material without OH bases, Nitrogen element without N-H bases in the derivative of polyalcohol
The water repellency chemical solution diluted,
(R1)aSi(H)bX1 4-a-b [1]
In formula [1], R1It is each independently of the others, is the carbon number optionally replaced comprising part or all of protium by fluorine element
For 1 valency organic group of 1~18 1 valency alkyl；In addition, X1It is each independently of the others, represents to be selected from the member by being bonded with element silicon
The element that element is 1 valency functional group of nitrogen, be bonded with element silicon is 1 valency functional group, halogen radical, itrile group and the-CO-NH-Si of oxygen
(CH3)3At least one kind of group in the group of composition；A is 1~3 integer, and b is 0~2 integer, and a and b's adds up to 1~3.
2. the cleaning method of chip according to claim 1, it is characterised in that the cleaning fluid is selected from by organic molten
It is at least one kind of in the group that agent, water, at least one kind of aqueous solution being mixed with water in organic solvent, acid, alkali, oxidant are constituted
Liquid.
3. the cleaning method of chip according to claim 1 or 2, it is characterised in that the water repellency chemical solution is included
Represented selected from the sulfonic acid and its acid anhydrides, following formulas [3] represented by hydrogen chloride, sulfuric acid, perchloric acid, phosphoric acid, following formulas [2]
It is carboxylic acid and its acid anhydrides, boron alkyl acid esters, aryl-boric acid ester, three (trifluoroacetyl epoxide) boron, tri-alkoxy boroxin, borontrifluoride
It is at least one kind of in the group for the silicon compound B compositions that boron, following formulas [4] are represented,
R2S(O)2OH [2]
In formula [2], R2It is the 1 valency alkyl that part or all of protium is optionally 1~18 by the carbon number that fluorine element replaces,
R3COOH [3]
In formula [3], R3It is the 1 valency alkyl that part or all of protium is optionally 1~18 by the carbon number that fluorine element replaces,
(R4)cSi(H)dX2 4-c-d [4]
In formula [4], R4It is each independently of the others, be the carbon number that is optionally replaced by fluorine element of part or all of protium for 1~
18 1 valency alkyl；In addition, X2It is each independently of the others, represents to be selected from by chloro ,-OCO-R5With-OS (O)2-R6In the group of composition
At least one kind of group, R5It is the 1 valency alkyl that part or all of protium is optionally 1~18 by the carbon number that fluorine element replaces,
R6It is the 1 valency alkyl that part or all of protium is optionally 1~18 by the carbon number that fluorine element replaces；C for 1~3 it is whole
Number, d is 0~2 integer, and c and d's adds up to 1~3.
4. the cleaning method of chip according to claim 1 or 2, it is characterised in that the water repellency chemical solution is included
Selected from by trimethyl silyl trifluoro-acetate, trimethylsilyl triflate, dimetylsilyl trifluoro
Acetic acid esters, dimetylsilyl triflate, Butyldimethylsilyl trifluoro-acetate, butyldimethyl silicon
Alkyl triflate, hexyl dimetylsilyl trifluoro-acetate, hexyl dimetylsilyl triflate,
Octyldimethyl silicyl trifluoro-acetate, octyldimethyl silicyl triflate, decyl dimethyl monosilane
Base trifluoro-acetate, decyl dimethyl silicyl triflate, dodecyl dimethyl silicyl trifluoro-acetate,
It is at least one kind of in the group of dodecyl dimethyl silicyl triflate composition.
5. the cleaning method of chip according to claim 1 or 2, it is characterised in that the silicon compound A is selected from by six
Methyl disilazane, trimethyl silyl dimethyl amine, trimethyl silyl diethylamide, tetramethyl-disilazane, two
Methyl silicane base dimethyl amine, dimetylsilyl diethylamide, 1,3- dibutyl tetramethyl-disilazane, butyl diformazan
Base silicyl dimethyl amine, Butyldimethylsilyl diethylamide, 1,3- dihexyls tetramethyl-disilazane, hexyl two
Methyl silicane base dimethyl amine, hexyl dimetylsilyl diethylamide, 1,3- dioctyls tetramethyl-disilazane, octyl group
Dimetylsilyl dimethyl amine, octyldimethyl silicyl diethylamide, 1,3- didecyls tetramethyl-disilazane, the last of the ten Heavenly stems
Base dimetylsilyl dimethyl amine, decyl dimethyl silicyl diethylamide, 1,3- bis- (dodecyl) tetramethyl two
Silazane, dodecyl dimethyl silicyl dimethyl amine, the group of dodecyl dimethyl silicyl diethylamide composition
In it is at least one kind of.
6. the cleaning method of chip according to claim 1 or 2, it is characterised in that the water repellency chemical solution is included
Selected from by ammonia, N, N, N ', N '-tetramethylethylenediamine, triethylenediamine, dimethylaniline, alkylamine, dialkylamine, trialkylamine,
It is at least one kind of in the group for the silicon compound C compositions that pyridine, piperazine, N- alkyl morpholines, following formulas [5] are represented,
(R7)eSi(H)fX3 4-e-f [5]
In formula [5], R7It is each independently of the others, be the carbon number that is optionally replaced by fluorine element of part or all of protium for 1~
18 1 valency alkyl；In addition, X3It is each independently of the others, is that the element being bonded with element silicon is for nitrogen and optionally first comprising fluorine element, silicon
The functional group of 1 valency of element；E is 1~3 integer, and f is 0~2 integer, and e and f's adds up to 1~3.
7. the cleaning method of chip according to claim 1 or 2, it is characterised in that make to supply in the process of the displacement
Water repellency chemical solution temperature be 70 DEG C of -10 DEG C of boiling points less than the water repellency chemical solution.
8. the cleaning method of chip according to claim 1 or 2, wherein, the esters are interior ester series solvent or carbonic acid
Ester series solvent.
9. a kind of water repellency chemical solution, its cleaning method in the chip any one of 1~claim 8 of claim
In use.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-293853 | 2010-12-28 | ||
| JP2010293853 | 2010-12-28 | ||
| JP2011-238623 | 2011-10-31 | ||
| JP2011238623 | 2011-10-31 | ||
| JP2011-274084 | 2011-12-15 | ||
| JP2011274084A JP2013118347A (en) | 2010-12-28 | 2011-12-15 | Cleaning method of wafer |
| CN201180063349.4A CN103283004B (en) | 2010-12-28 | 2011-12-20 | Wafer washing method |
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| CN201180063349.4A Division CN103283004B (en) | 2010-12-28 | 2011-12-20 | Wafer washing method |
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| CN107068540A true CN107068540A (en) | 2017-08-18 |
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| CN201611162059.6A Pending CN107068540A (en) | 2010-12-28 | 2011-12-20 | The cleaning method of chip |
| CN201180063349.4A Active CN103283004B (en) | 2010-12-28 | 2011-12-20 | Wafer washing method |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201180063349.4A Active CN103283004B (en) | 2010-12-28 | 2011-12-20 | Wafer washing method |
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| Country | Link |
|---|---|
| JP (1) | JP2013118347A (en) |
| KR (1) | KR101593517B1 (en) |
| CN (2) | CN107068540A (en) |
| SG (3) | SG10201710240SA (en) |
| TW (1) | TWI440993B (en) |
| WO (1) | WO2012090779A1 (en) |
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| CN110875172A (en) * | 2018-08-30 | 2020-03-10 | 东芝存储器株式会社 | Substrate processing method and method for manufacturing semiconductor device |
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| JP7189427B2 (en) * | 2017-12-22 | 2022-12-14 | セントラル硝子株式会社 | Surface treatment agent and method for producing surface treated body |
| JP6916731B2 (en) * | 2017-12-28 | 2021-08-11 | 東京応化工業株式会社 | A method for making a substrate water repellent, a surface treatment agent, and a method for suppressing the collapse of an organic pattern or an inorganic pattern when cleaning the substrate surface with a cleaning liquid. |
| US11282709B2 (en) | 2018-01-15 | 2022-03-22 | Central Glass Company, Limited | Chemical agent for forming water repellent protective film and surface treatment method for wafers |
| JP7277700B2 (en) * | 2018-01-15 | 2023-05-19 | セントラル硝子株式会社 | Chemical solution for forming water-repellent protective film and method for surface treatment of wafer |
| JP7252478B2 (en) * | 2018-04-05 | 2023-04-05 | セントラル硝子株式会社 | WAFER SURFACE TREATMENT METHOD AND COMPOSITION USED IN THIS METHOD |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20130088896A (en) | 2013-08-08 |
| CN103283004A (en) | 2013-09-04 |
| SG10201710240SA (en) | 2018-01-30 |
| TW201232196A (en) | 2012-08-01 |
| CN103283004B (en) | 2017-04-12 |
| SG10201605687VA (en) | 2016-09-29 |
| TWI440993B (en) | 2014-06-11 |
| SG190068A1 (en) | 2013-06-28 |
| WO2012090779A1 (en) | 2012-07-05 |
| KR101593517B1 (en) | 2016-02-15 |
| JP2013118347A (en) | 2013-06-13 |
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