CN109976108A - A kind of cleaning solution for semiconductor - Google Patents
A kind of cleaning solution for semiconductor Download PDFInfo
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- CN109976108A CN109976108A CN201711439519.XA CN201711439519A CN109976108A CN 109976108 A CN109976108 A CN 109976108A CN 201711439519 A CN201711439519 A CN 201711439519A CN 109976108 A CN109976108 A CN 109976108A
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- Prior art keywords
- acid
- cleaning solution
- fluoride
- ammonium
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- General Physics & Mathematics (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The present invention proposes a kind of cleaning solution for semiconductor, contains: fluoride, organic amine, water, nitrogenous polyacid and organic reducing acid and its salt.Cleaning solution cleaning ability of the invention is strong, can effectively remove plasma etching residues during manufacture of semiconductor, the residue after being ashed especially in copper Ma Shige technique.
Description
Technical field
The present invention relates to cleaning solution technical field more particularly to a kind of cleaning solutions for semiconductor.
Background technique
In semiconductor components and devices manufacturing process, photoresist coating, exposure and imaging are for the manufacture of the pattern of component
It is necessary Patternized technique step.Usual patterned step is to serve as a contrast the thin film coated of photoresist in designed chip
Resulting image on the thin film by circuit design is transferred to usually electricity Jie by exposure, development, plasma etching by bottom
The subsurface material of matter or metal.Plasma etch processes technique bring is as a result, photoresist, etching gas and etched material
Product be deposited on around the bottom sidewall of chip or substrate upper channel as organic and inorganic and oxide residue or upper table
Face.Before carrying out next processing step, these residues through plasma etching process must be removed all, fail to go completely
Except the interruption of meeting generation circuit or aisle resistance increase and make the consequence of component failure.Semiconductor microelectronic manufactures integrated horizontal at present
It is continuously improved that patterned Size of Microelectronic Devices is smaller and smaller, the size in channel is also smaller and smaller, and cleaning solution can not only be gone
Except the residue for remaining in channel upper surface, to have excellent wetability also smoothly to remove the residual of deep channel bottom
Object.Therefore the exploitation of low viscosity cleaning solution is also more and more important.Simultaneously as semiconductor fabrication process cost control is lower and lower,
It also requires to improve to the cleaning solution through plasma etching process residue can be effectively removed, is effectively removing such residue
While cost can be greatly lowered and be a problem to be solved.
US6,224,785 disclose the fluorine-containing cleaning combination that a kind of pair of copper has extremely low corrosion, although the cleaning solution is to copper
Protection it is very good, there is no corrosion to inhibit adsorption problem, but the viscosity of its cleaning solution and surface tension are all very big,
To influence cleaning effect, industry is also it is often found that after use there is spherical residue in the phase.US 5,972,862 is public
The cleaning combination of fluorine-containing material is opened comprising fluorine-containing material, inorganic or organic acid, quaternary ammonium salt and organic polar solvent, pH
It is 7~11, since its cleaning effect is not to be stabilized very much problem.US8,481,472 discloses a kind of double to copper for removing
The high aqueous fluorine-containing acidic cleaning solution of Damascus technics residue, the cleaning liquid water content are more than 70%, and control solution is acid
Property condition, although metal and nonmetallic cost can be protected to be relatively low simultaneously, for the residue removal of organic species
Effect is undesirable.
Therefore, in order to overcome the defect of existing cleaning solution, adapt to new cleaning requirement, for example, cleaning fluid viscosity reduce, at
This reduction, environment is more friendly, overcomes metal corrosion inhibitor adsorption, low defect level, low etching rate and is suitable for
High revolving speed rotation washes down mode etc., it would be highly desirable to seek new cleaning solution.
Summary of the invention
To solve the above problems, the present invention proposes a kind of cleaning solution for semiconductor, contain: fluoride, organic amine,
Water, nitrogenous polyacid and organic reducing acid and its salt.Cleaning solution cleaning ability of the invention is strong, can effectively remove semiconductor system
Plasma etching residues during journey, the residue after being ashed especially in copper Ma Shige technique.
Specifically, the present invention discloses a kind of cleaning solution for semiconductor comprising, it is fluoride, organic amine, nitrogenous polynary
Acid, organic reducing acid and its salt, Yi Jishui.
Preferably, the fluoride is selected from hydrogen fluoride (HF), ammonium fluoride (NH4F), ammonium acid fluoride (NH4HF2), tetramethyl fluorine
Change ammonium (N (CH3)4) and trihydroxyethyl ammonium fluoride (N (CH F2OH)3HF one of) or a variety of, the alkali includes ammonium hydroxide, quaternary amine
One of hydroxide and hydramine are a variety of.
Preferably, the mass percent concentration of the fluoride is 0.01~20%.
Preferably, the organic amine is selected from monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, N, N- dimethyl second
One of hydramine, N methyldiethanol amine, diethylenetriamine, triethylene tetramine, pentamethyl-diethylenetriamine, polyethylene polyamine
Or it is a variety of；It is further preferred that the organic amine is selected from pentamethyl-diethylenetriamine, monoethanolamine, isopropanolamine and triethanolamine
One of or it is a variety of.
Preferably, the mass percent concentration of the organic amine is 20~60%.
Preferably, the nitrogenous polyacid is selected from iminodiacetic acid, N- methyliminodiacetic acid, N- ethoxy second two
Amine triacetic acid, l-cysteine, N- (2- acetamide) -2- iminodiacetic acid, diethylenetriamine pentaacetic acid, nitrilotriacetic acid, ethylenediamine
One of tetraacethyl is a variety of.
Preferably, the mass percent concentration of the nitrogenous polyacid is 1~10%.
Preferably, the organic reducing acid and its salt are selected from citric acid, ammonium citrate, oxalic acid, ammonium oxalate, L- Vitamin C
Acid, D- ascorbic acid, benzene sulfonic acid, ammonium benzene sulfonate, p-aminobenzene sulfonic acid, methyl sulfinate, trifluoromethane sulfonic acid, methanesulfonic acid, first
One of base ichthyodin is a variety of.
Preferably, the mass percent concentration of the organic reducing acid and its salt is 0.5~10%；It is further preferred that
The mass percent concentration of the organic reducing acid and its salt is 1-5%.
Preferably, the mass percent concentration of the water is 35~70%.
Compared with prior art, the technical advantages of the present invention are that:
1) cleaning solution cleaning ability of the invention is strong, and plasma etching remains during can effectively removing manufacture of semiconductor
Object, the residue after being ashed especially in copper Ma Shige technique；
2) present invention makes cleaning solution in height by nitrogenous polyacid and organic reducing acid and its effective complex role of salt
There is lesser corrosion rate to nonmetallic materials (such as silicon oxynitride) and metal material (such as Cu) in the cleaning of revolving speed single-chip microcontroller, fits
For batch immersion type, batch rotating spraying formula cleaning way, it is particularly suitable for the high revolving cleaning way of revolving speed monolithic；
3) present invention is significantly reduced compared with existing market product cost and viscosity, has larger action pane, in semiconductor die
The microelectronic fields such as piece cleaning have a good application prospect.
Specific embodiment
Below with reference to table and specific embodiment, advantage of the invention is elaborated.
Agents useful for same and raw material of the present invention are commercially available.According to each component and its content cited in table 1, mix to
Substantially uniformity can then obtain meeting the preferred embodiment of the present invention, specific as shown in table 1.
1 comparative example of table and with meeting the preferred embodiment of the present invention component and content
The section Example and comparative example in table 1 are chosen, tests the viscosity of the section Example and comparative example respectively；With city
The field prior art cost of raw material is as basic unit, by the cleaning solution cost of raw material of the invention divided by prior art raw material
The ratio of cost enumerates the relative cost of cleaning solution of the present invention as relative cost；After observation cleaning, each cleaning solution is to metal
With the corrosion condition of nonmetallic materials, and to the gold containing plasma etching residues under monolithic high speed rotation cleaning way
Belong to the cleaning situation in duct.
Wherein, specific cleaning step and condition are as follows: nonmetallic (SiON) bare silicon wafer is immersed in cleaning solution respectively,
30min is impregnated at 40 DEG C, is dried up after deionized water rinses with high pure nitrogen, rate of metal corrosion is tested；By metal (Cu) sky
White silicon wafer uses single chip washer, cleans 10min under 40 DEG C and 400rpm of revolving speed, uses High Purity Nitrogen after deionized water rinses
Air-blowing is dry, tests nonmetallic corrosion rate.By the metal duct wafer in Damascus technics containing plasma etching residues
It is placed under high speed rotation cleaning way, rotates 1.5min at 25 DEG C to 50 DEG C, High Purity Nitrogen air-blowing is used after deionized water rinses
Dry, the cleaning effect and each cleaning solution for observing residue obtain concrete outcome such as 2 institute of table to metal and nonmetallic corrosion condition
Show.
The wash result table of comparisons of 2 section Example of table and comparative example
It infuses, in table 2, Cu is copper；SiON is silicon nitride.
From Table 2, it can be seen that the present embodiment 6 is compared to right in the case where its special component and its essentially identical content
Ratio 6-1 joined organic reducing acid；And comparative example 6-1 then the organic reducing acid amount not being added is added into it is nitrogenous polynary
On acid, there is the phenomenon that copper corrosion rate is big, and Damascus technics flushing channel size broadens in comparative example 6-1, and embodiment 6
Comparative example 6-1 then is far smaller than to the corrosion rate of copper, and without changing channel size；In addition, comparative example 6-2 and embodiment 6
Comparison in as can be seen that comparative example 6-2 compared to the embodiment of the present invention 6 nitrogenous polyacid is not added, and the amount not being added
It is added on organic reducing acid, it is big that copper corrosion rate also occurs in comparative example 6-2, and Damascus technics flushing channel size becomes
Wide phenomenon.To, from the above, it can be seen that, pass through nitrogen polyacid and organic reducing acid complex role in cleaning solution of the present invention,
Corrosion of metal can be effectively controlled, the size of Damascus technics flushing channel is not changed.
Comparative example 16-1 is using the fluorine-containing cleaning solution of (US 6,224,785) that is disclosed, with the embodiment in the present invention
It compares, nitrogenous polyacid and organic reducing acid is not added, is added to acetyl acetamide as metal corrosion inhibitor, and
The organic reducing acid selected in non-present invention, although can control metal and nonmetallic corrosion, comparative example 16-1
Cleaning fluid viscosity it is larger, Damascus technics crystal column surface cleaning in there is a small amount of spheric granules, influence cleaning effect；It is right
Ratio 16-2 joined nitrogenous polyacid, organic reducing acid of the invention not be added, the cleaning solution is to rate of metal corrosion
More than the corrosion rate (< 5A/min) controlled in the industry, and the cleaning fluid viscosity is high, can not solve to generate on wafer after cleaning spherical
The problem of particle, while the cost of the cleaning solution is higher than existing product in the market.N- cyclohexyl pyrrole is added in comparative example 17
Pyrrolidone reduces the viscosity of cleaning solution as solvent, although while joined 2- hydroxyethylhydrazine also can control to metal and Fei Jin
Belonging to corrosion condition and reduces the viscosity of cleaning solution to a certain degree, cleaning effect is also relatively preferable, but due to its higher cost, no
Conducive to semiconductor fabrication process cost optimization is realized, it can not achieve and be widely used to promote.
Simultaneously from Table 2, it can be seen that cleaning solution of the invention to semiconductor be made used in metal (such as Cu) and non-
Metal (SiON) will not corrode substantially, and corrosion rate is close to or smaller than semiconductor industry and usually cleans in monolithic high speed rotation
Required by lowerWith
Meanwhile cleaning solution of the invention is significantly reduced compared with existing market product cost and viscosity, by nitrogenous polyacid and
Organic reducing acid and its effective complex role of salt can effectively remove plasma etching in semiconductor Damascus technics and remain
Object and to metal and it is nonmetallic do not generate corrosion, have a good application prospect in fields such as cleaning semiconductor chips.
It should be understood that % of the present invention refers to mass percentage concentration.
It should be noted that the embodiment of the present invention has preferable implementation, and not the present invention is made any type of
Limitation, any one skilled in the art change or are modified to possibly also with the technology contents of the disclosure above equivalent effective
Embodiment, as long as without departing from the content of technical solution of the present invention, it is to the above embodiments according to the technical essence of the invention
Any modification or equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (13)
1. a kind of cleaning solution for semiconductor, which is characterized in that including fluoride, organic amine, nitrogenous polyacid are organic to go back
Originality acid and its salt, Yi Jishui.
2. cleaning solution as described in claim 1, which is characterized in that
The fluoride is selected from the salt that hydrogen fluoride and/or hydrogen fluoride and alkali are formed.
3. cleaning solution as claimed in claim 2, which is characterized in that
The fluoride is selected from hydrogen fluoride (HF), ammonium fluoride (NH4F), ammonium acid fluoride (NH4HF2), Methanaminium, N,N,N-trimethyl-, fluoride (N (CH3)4) and trihydroxyethyl ammonium fluoride (N (CH F2OH)3HF one of) or a variety of, the alkali includes ammonium hydroxide, quaternary ammonium hydroxide and alcohol
One of amine is a variety of.
4. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the fluoride is 0.01~20%.
5. cleaning solution as described in claim 1, which is characterized in that
The organic amine is selected from monoethanolamine, diethanol amine, triethanolamine, isopropanolamine, N, N- dimethylethanolamine, N- methyl
One of diethanol amine, diethylenetriamine, triethylene tetramine, pentamethyl-diethylenetriamine, polyethylene polyamine are a variety of.
6. cleaning solution as claimed in claim 5, which is characterized in that
The organic amine is selected from one of pentamethyl-diethylenetriamine, monoethanolamine, isopropanolamine and triethanolamine or a variety of.
7. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the organic amine is 20~60%.
8. cleaning solution as described in claim 1, which is characterized in that
The nitrogenous polyacid is selected from iminodiacetic acid, N- methyliminodiacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, L-
Cystine, N- (2- acetamide) -2- iminodiacetic acid, diethylenetriamine pentaacetic acid, nitrilotriacetic acid, one in ethylenediamine tetra-acetic acid
Kind is a variety of.
9. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the nitrogenous polyacid is 1~10%.
10. cleaning solution as described in claim 1, which is characterized in that
The organic reducing acid and its salt are selected from citric acid, ammonium citrate, oxalic acid, ammonium oxalate, L-AA, D- Vitamin C
Acid, benzene sulfonic acid, ammonium benzene sulfonate, p-aminobenzene sulfonic acid, methyl sulfinate, trifluoromethane sulfonic acid, methanesulfonic acid, in methane sulfonic acid ammonium
It is one or more.
11. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the organic reducing acid and its salt is 0.5~10%.
12. cleaning solution as claimed in claim 11, which is characterized in that
The mass percent concentration of the organic reducing acid and its salt is 1-5%.
13. cleaning solution as described in claim 1, which is characterized in that
The mass percent concentration of the water is 35~70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711439519.XA CN109976108A (en) | 2017-12-27 | 2017-12-27 | A kind of cleaning solution for semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711439519.XA CN109976108A (en) | 2017-12-27 | 2017-12-27 | A kind of cleaning solution for semiconductor |
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| Publication Number | Publication Date |
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| CN109976108A true CN109976108A (en) | 2019-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201711439519.XA Pending CN109976108A (en) | 2017-12-27 | 2017-12-27 | A kind of cleaning solution for semiconductor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114038942A (en) * | 2021-11-08 | 2022-02-11 | 浙江光特科技有限公司 | Etching photoresist removing method for photoelectric detector chip |
| CN117684182A (en) * | 2023-12-13 | 2024-03-12 | 中铜华中铜业有限公司 | A kind of copper strip surface cleaning agent and preparation method thereof |
| CN120248991A (en) * | 2025-04-14 | 2025-07-04 | 四川奥瑞特化学试剂有限公司 | Oxalic acid solution for decontamination of photovoltaic devices and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1904016A (en) * | 2005-06-23 | 2007-01-31 | 气体产品与化学公司 | Composition for removal of residue comprising cationic salts and methods using same |
| CN101597548A (en) * | 2008-06-06 | 2009-12-09 | 安集微电子科技(上海)有限公司 | A plasma etch residue cleaning solution |
| CN101957563A (en) * | 2009-07-13 | 2011-01-26 | 安集微电子（上海）有限公司 | Fluorine-containing plasma etching residue cleaning solution |
| CN103777475A (en) * | 2012-10-23 | 2014-05-07 | 气体产品与化学公司 | Cleaning Formulation |
| CN106547178A (en) * | 2015-09-23 | 2017-03-29 | 气体产品与化学公司 | cleaning preparation |
-
2017
- 2017-12-27 CN CN201711439519.XA patent/CN109976108A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1904016A (en) * | 2005-06-23 | 2007-01-31 | 气体产品与化学公司 | Composition for removal of residue comprising cationic salts and methods using same |
| CN101597548A (en) * | 2008-06-06 | 2009-12-09 | 安集微电子科技(上海)有限公司 | A plasma etch residue cleaning solution |
| CN102047184A (en) * | 2008-06-06 | 2011-05-04 | 安集微电子科技(上海)有限公司 | A plasma etch residue cleaning solution |
| CN101957563A (en) * | 2009-07-13 | 2011-01-26 | 安集微电子（上海）有限公司 | Fluorine-containing plasma etching residue cleaning solution |
| CN103777475A (en) * | 2012-10-23 | 2014-05-07 | 气体产品与化学公司 | Cleaning Formulation |
| CN106547178A (en) * | 2015-09-23 | 2017-03-29 | 气体产品与化学公司 | cleaning preparation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114038942A (en) * | 2021-11-08 | 2022-02-11 | 浙江光特科技有限公司 | Etching photoresist removing method for photoelectric detector chip |
| CN117684182A (en) * | 2023-12-13 | 2024-03-12 | 中铜华中铜业有限公司 | A kind of copper strip surface cleaning agent and preparation method thereof |
| CN120248991A (en) * | 2025-04-14 | 2025-07-04 | 四川奥瑞特化学试剂有限公司 | Oxalic acid solution for decontamination of photovoltaic devices and preparation process thereof |
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