CN107300839B - A kind of fluorine-containing plasma etching residue cleaning, preparation method and application - Google Patents

A kind of fluorine-containing plasma etching residue cleaning, preparation method and application Download PDF

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CN107300839B
CN107300839B CN201710611867.4A CN201710611867A CN107300839B CN 107300839 B CN107300839 B CN 107300839B CN 201710611867 A CN201710611867 A CN 201710611867A CN 107300839 B CN107300839 B CN 107300839B
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cleaning solution
mass fraction
preparation
acid
dispersing agent
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CN107300839A (en
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王溯
蒋闯
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Shanghai Xinyang Semiconductor Material Co Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/426Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides

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  • General Physics & Mathematics (AREA)
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  • Cleaning Or Drying Semiconductors (AREA)

Abstract

The invention discloses a kind of fluorine-containing plasma etching residue cleaning, preparation method and applications.The preparation method of cleaning solution of the invention comprising the following steps: following raw materials are mixed;The raw material includes following component: dispersing agent, fluoride, organic solvent, corrosion inhibiter, organic amine and water;Wherein, the dispersing agent is polycarboxylic acid dispersant and/or organic phosphine dispersing agent.Cleaning solution made from preparation method of the invention is placed for a long time and hardly happens reunion in use process, does not generate particle substantially, and particle incrementss are small, cleaning quality and effect are good.

Description

A kind of fluorine-containing plasma etching residue cleaning, preparation method and application
Technical field
The present invention relates to a kind of chemical reagent for semiconductor fabrication, and in particular to a kind of fluorine-containing plasma etching Residual washing liquid, preparation method and application.
Background technique
In the production technology of semiconductor integrated circuit, deposit is needed to form multiple figuratum semiconductor layers, conductor layer And insulation material layer.Photoresist is applied on inorganic substrate, by exposing and subsequent development shape on the photoresist At pattern, the pattern of formation is then used as exposure mask.The etching for the inorganic substrate part that do not sheltered by photoresist pattern Method be exposed to metal etch containing under fluoro plasma to remove the metal of exposure to forming fine circuitry.Scheme being formed After case, deposit and etching, it is necessary to thoroughly remove photoresist layer before next processing step.
Fluorine-containing plasma ashing can remove photoresist, but leave the residue after ashing on substrate, usually adopt It is removed with fluorine-containing plasma etching residual washing liquid.As the geometric proportion of component in semiconductor device structure persistently becomes Small, under the chip line width lower than 0.13 μm, the clean level of cleaning solution is most important.
Therefore, although existing fluorine-containing plasma etching residue cleaning is widely used during removing removal of residue, But cleaning solution is placed for a long time and use process can generate particle because of reunion, and particle incrementss are big, and in cleaning process, cleaning Particle present in liquid is not easy to rinse out from chip surface, influences cleaning effect.Also, this particle stays in chip surface meeting Cause circuit pollution, and causes uncertain conductive failure.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome existing fluorine-containing plasma etching residue cleaning long Phase, which places, generates particle by reuniting in use process, and particle incrementss are big, influence cleaning effect, so that cleaning effect is bad The problems such as, and provide a kind of fluorine-containing plasma etching residue cleaning, preparation method and application.Preparation side of the invention Cleaning solution made from method is placed for a long time and hardly happens reunion in use process, does not generate particle, and particle incrementss substantially Small, cleaning quality and effect are good.
The present invention provides a kind of cleaning solutions, are made by following raw materials, and the raw material includes following component: dispersion Agent, fluoride, organic solvent, corrosion inhibiter, organic amine and water;Wherein, the dispersing agent is polycarboxylic acid dispersant and/or has Machine phosphine dispersing agent.
Wherein, the mass fraction of the dispersing agent is preferably 0.01%-5% (more preferably 2%-4%;Most preferably 2.5%-3.5%).The mass fraction of the fluoride is preferably 0.05%-20% (more preferably 2.5%-15%;It is optimal It is selected as 3~10%).The mass fraction of the organic solvent is preferably 10%-65% (more preferably 30%-50%;Most preferably It is 35~45%).The mass fraction of the corrosion inhibiter is preferably 0.01%-10% (more preferably 0.5%-5%;Most preferably It is 1%~3%).The mass fraction of the organic amine is preferably 5%-40% (more preferably 13%-25%;Most preferably 15%-20%).
Wherein, in the cleaning solution, the dosage that the sum of each component mass fraction is 100%, Gu Shui is preferably each to supply The sum of constituent mass score is 100% meter.
Wherein, the polycarboxylic acid dispersant and organic phosphine dispersing agent are preferably non-salt dispersing agent.It is described Polycarboxylic acid dispersant be preferably polyacrylic acid, hydrolysis of polymaleic anhydride, maleic acid-acrylic acid copolymer and acrylic acid hydroxypropyl One of ester copolymer is a variety of (such as two kinds), more preferably polyacrylic acid and/or hydrolysis of polymaleic anhydride.Described is poly- The weight average molecular weight of carboxylic acids dispersing agent preferably 600~70000;More preferably 1500~10000.Organic phosphine dispersion Agent be preferably aminotrimethylenephosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, Hexapotassium, polyamino polyether base methylenephosphonic acid, double 1,6 hexamethylene triamine, five methylenephosphonic acids, phosphonobutane -1 2-, One of 2,4- tricarboxylic acids, Polyol Phosphate and 2- hydroxyphosphonoacetic acid are a variety of (such as two kinds), more preferably ammonia Three methylenephosphonic acid of base, 1-hydroxy ethylidene-1,1-diphosphonic acid, diethylene triamine pentamethylene phosphonic, ethylene diamine tetra methylene phosphonic acid and polyamino polyether Any two kinds of mixture in base methylenephosphonic acid;Most preferably aminotrimethylenephosphonic acid and/or 1-hydroxy ethylidene-1,1-diphosphonic acid.
Wherein, the fluoride can be the fluoride of this field routine, preferably the salt and/or hydrogen of hydrofluoric acid and alkali formation Fluoric acid.Wherein, the alkali is one of ammonia (such as ammonium hydroxide or ammonia), unitary hydramine, polyhydric alcohol amine and quaternary ammonium base or more Kind (such as two kinds).In the more preferable ammonium fluoride of the fluoride, ammonium acid fluoride, Methanaminium, N,N,N-trimethyl-, fluoride and trihydroxyethyl ammonium fluoride It is one or more.
Wherein, the organic solvent can be this field routine organic solvent, preferably sulfoxide type solvents, sulfone class solvent, One of ether solvent, alcohols solvent, amide solvent, ketones solvent and esters solvent are a variety of (such as two kinds).It is described Sulfoxide type solvents be preferably dimethyl sulfoxide.The sulfone class solvent is preferably sulfolane.The ether solvent is preferably third Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol two One of ether is a variety of (such as two kinds).The amide solvent is preferably dimethylformamide and/or dimethyl second Amide.The alcohols solvent is preferably propylene glycol and/or diethylene glycol.The ketones solvent be preferably acetone, methyl ethyl ketone, One of imidazolidinone, pyrrolidones and imidazolone are a variety of (such as two kinds).The preferred lactic acid second of the esters solvent Ester and/or ethyl acetate.Preferably, the imidazolidinone is preferably 1,3- dimethyl -2- imidazolidinone.The pyrrolidines Ketone is preferably N-Methyl pyrrolidone and/or hydroxyethyl-pyrrolidone;The imidazolone is preferably 1,3- dimethyl -2- miaow Oxazoline ketone.
The corrosion inhibiter is the corrosion inhibiter of this field routine, preferably 1,2-diaminocyclohexane tetraacetic acid, benzotriazole, imino group Oxalic acid, urea, citric acid, sulfamic acid, ethylenediamine tetra-acetic acid, phenyl hydrazones compound, ketone hydrazone compounds, dithizone class Close one of object and kappa hydrazone compounds or a variety of (such as two kinds).The preferred acetophenone phenylhydrazone of the phenyl hydrazones compound, One of acetone phenylhydrazone and acetone 2,4- dinitrophenylhydrazone are a variety of (such as two kinds).The preferred hexichol of ketone hydrazone compounds Ketone hydrazone.The preferred Diphenylthiocarbazone of dithizone class compound.The preferred diphenylcarbazide of kappa hydrazone compounds Bar hydrazone.
Wherein, the organic amine can be the organic amine of this field routine, preferably monoethanolamine, diglycolamine, isopropyl One of hydramine, triethanolamine, hexa and pentamethyl-diethylenetriamine are a variety of (such as two kinds).
Wherein, one of the preferred deionized water of the water, distilled water, pure water and ultrapure water or a variety of (such as two kinds).
In a preferred embodiment of the invention, the cleaning solution is made by following raw materials, the raw material components It is made of dispersing agent, fluoride, organic solvent, corrosion inhibiter, organic amine and water.
The present invention also provides the preparation methods of the cleaning solution described in one kind comprising the following steps: by the raw material Mixing.The mixed temperature is room temperature.After the mixing, oscillation, the behaviour of filtering are preferably further comprised Make.The purpose of oscillation is to be sufficiently mixed each raw material component, and hunting speed and time are unlimited.Filtering is insoluble in order to remove Object.
The present invention also provides application of the cleaning solution described in one kind in the semiconductor chip after etching ashing.Institute The semiconductor chip of the preferred copper-connection of the semiconductor chip stated or aluminium interconnection structure.
The application preferably includes the following steps: the semiconductor chip after etching ashing is contacted with the cleaning solution ?.More preferably include the following steps: the semiconductor chip after etching ashing is contacted with the cleaning solution, vibrates, washed, Drying.
Wherein, preferably 10 DEG C -90 DEG C of the temperature of the contact, preferably 20 DEG C -60 DEG C, such as 40-45 DEG C.Described connects The operation of touching preferably immerses the semiconductor chip after etching ashing in the cleaning solution.The oscillation is preferably shaken in constant temperature It swings in device and vibrates.Preferably 10 DEG C -90 DEG C of the temperature of the oscillation, preferably 20 DEG C -60 DEG C, such as 40-45 DEG C.The washing It is preferred that being washed with water (such as one of deionized water, distilled water, pure water and ultrapure water or a variety of).The method of the drying It is preferred that being dried up with high-purity nitrogen.
Room temperature refers to 10-30 DEG C in the present invention.
In the present invention, the mass fraction refers to that the quality of each component accounts for the percentage of all components gross mass.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: cleaning solution made from preparation method of the invention is placed and was used for a long time Reunion is hardly happened in journey, does not generate particle substantially, and particle incrementss are small, and cleaning quality and effect are good.And it is of the invention Cleaning solution made from preparation method can use in wider temperature range, such as 10 DEG C -90 DEG C.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient The selection of product specification.
In following embodiment and comparative examples, the preparation method of cleaning solution includes the following steps: to mix corresponding raw material, i.e., It can.
In following embodiments, concrete operations temperature is not limited, is each meant and is carried out at room temperature.
Embodiment 1-49
Table 1
Table 2
Comparative example 1-12
Table 3
Table 4
Comparative example 13-18
Effect example
1, cleaning solution places situation
After cleaning solution made from the various embodiments described above and comparative example is placed 12 months, the case where its particle increases is detected.
Step (1), that cleaning solution made from the various embodiments described above and comparative example is tested using KS-42A granulometer Grain initial value;
Step (2) will be placed in 1 gallon of high-purity bucket after the filtering of cleaning solution made from the various embodiments described above and comparative example, Constant temperature is placed 12 months to 30 DEG C, after test 12 months in cleaning solution 0.1 μm of particle data, calculate the increase of cleaning solution particle Situation.
2, it the semiconductor chip concrete operations after etching ashing: will be cleaned made from the various embodiments described above and comparative example After liquid filtering, 50L is taken to be placed in cleaning machine, semiconductor chip 2 after etching ashing immersed in the cleaning solution (every Hour cleaning two panels, is cleaned 50 hours totally by 100).Without filtering in cleaning process.The oscillation is shaken in constant temperature oscillator It swings.The temperature of the oscillation is 40 DEG C.The washing is washed with deionized.High-purity nitrogen air-blowing is used in the drying It is dry.Wash result is shown in Table 5.
3, cleaning solution made from the various embodiments described above and comparative example tests the corrosive effect of blank wafer
Cleaning solution made from the various embodiments described above and comparative example is used to clean blank Ti chip, measures its corrosion to Ti Situation.Test method and condition: by 4 × 4cm blank Ti chip immerse cleaning solution, at 20-60 DEG C using constant temperature oscillator with About 60 revs/min of vibration frequency vibrates 60 minutes, is then dried up after deionized water is washed with high pure nitrogen, utilizes quadrupole probe The variation of instrument measurement blank Ti chip etching front and rear surfaces resistance is calculated.
Cleaning solution made from the various embodiments described above and comparative example is used to clean blank Cu chip, measures its corruption for Cu Lose situation.Test method and condition: 4 × 4cm blank Ti chip is immersed into cleaning solution, constant temperature oscillator is utilized at 20-60 DEG C It is vibrated 60 minutes with about 60 revs/min of vibration frequency, is then dried up after deionized water is washed with high pure nitrogen, visited using quadrupole The variation of needle instrument measurement blank Cu chip etching front and rear surfaces resistance is calculated.
Cleaning solution made from the various embodiments described above and comparative example is used to clean blank Al chip, measures it for metal Al Corrosion condition.Test method and condition: 4 × 4cm blank Al chip is immersed into cleaning solution, is shaken at 20-60 DEG C using constant temperature It swings device to vibrate 60 minutes with about 60 revs/min of vibration frequency, is then dried up after deionized water is washed with high pure nitrogen, utilize four The variation of pole probe machine measurement blank Al chip etching front and rear surfaces resistance is calculated.
The tetraethoxysilane (TEOS) for being used to clean blank for cleaning solution made from the various embodiments described above and comparative example is brilliant Piece measures it for the corrosion condition of nonmetallic TEOS.Test method and condition: 4 × 4cm blank TEOS chip is immersed and is cleaned Liquid is vibrated 60 minutes with about 60 revs/min of vibration frequency using constant temperature oscillator at 20~60 DEG C, is then washed through deionization It is dried up after washing with high pure nitrogen.Utilize the change of TEOS thickness before and after Nanospec6100 calibrator measurement blank TEOS wafer cleaning Change is calculated.
Every test result is shown in Table 5.
DX1-DX12 --- contrast effect example 1-18 respectively corresponds the effect data of cleaning solution in comparative example 1-18;
X1-X49 --- effect example 1-49 respectively corresponds the effect data of cleaning solution in embodiment 1-49.
Table 5
Each symbol meaning of table 6
Clean situation: ◎ is completely removed Corrosion condition: ◎ no corrosion
Zero is a small amount of remaining Zero slightly corrodes
The more remnants of Δ Δ moderate corrosion
× abundant residues × heavy corrosion
It is right in addition to requiring cleaning solution that can effectively remove photoresist residue in the production technology of semiconductor integrated circuit The metal that touches and it is nonmetallic have other than compatibility well, after the completion of also requiring cleaning, cleaning solution is easily from chip Surface washing is clean.Therefore the clean level of cleaning solution itself is most important, and this requires particle increases cleaning solution after use It measures small.
It can be seen that the cleaning solution of comparative example 1-12 from above-mentioned contrast effect example DX1-DX18 and effect example X1-X49 Raw material components in lack dispersing agent, the dispersing agent in the raw material components of the cleaning solution of comparative example 13-18 is not organic phosphine point Powder and/or polycarboxylic acid dispersant, specially sodium salt dispersing agent or glyceride type dispersing agent, stearoyl amine dispersing agent, Its cleaning solution obtained is easy to occur to reunite after standing and cleaning and generates a large amount of particles, these particles are not easy from chip surface It rinses out, circuit pollution can be caused, and uncertain conductive failure can be caused.Cleaning solution made from comparative example 1-18 is quiet After setting December, 0.1 μm of particle of cleaning solution increases number in 5000particles/mL or more, even up to 12000particles/mL or more.After cleaning chip, 0.1 μm of particle of cleaning solution increase number 85000particles/mL with On, even up to 240000particles/mL or more.
And in the raw material components of cleaning solution of the invention, due to being added to dispersing agent, cleaning solution obtained is either stood Or it is not easy to reunite after cleaning chip, it not will form a large amount of particle, easily rinsed out from chip surface, circuit will not be caused Pollution, and uncertain conductive failure will not be caused.In particular, the raw material components of cleaning solution of the invention include organic phosphine When class dispersing agent, after standing December, 0.1 μm of particle of cleaning solution increases number in 100~250particles/mL, cleans chip 0.1 μm of particle of cleaning solution increases number in 300~500particles/mL afterwards;The raw material components of cleaning solution of the invention include poly- When carboxylic acids dispersing agent, after standing December, 0.1 μm of particle of cleaning solution increases number in 300~500particles/mL, cleaning 0.1 μm of particle of cleaning solution increases number in 500~1000particles/mL after chip.As it can be seen that cleaning solution of the invention is reducing Or inhibits to stand and occur in terms of reuniting and generating a large amount of particles after cleaning, significant effect.
From above-mentioned contrast effect example DX1-DX18 and effect example X1-X49 it can also be seen that either cleaning effect, Or to metal and nonmetallic corrosion condition, cleaning solution of the invention has promotion compared to the cleaning solution of comparative example, this is also anti- Agglomerated particle has been reflected to have a certain impact for cleaning effect.

Claims (8)

1. a kind of preparation method of cleaning solution, which is characterized in that it includes the following steps: to mix following raw materials;It is described Raw material include following component: dispersing agent, fluoride, organic solvent, corrosion inhibiter, organic amine and water;Wherein, the dispersing agent For organic phosphine dispersing agent;Organic phosphine dispersing agent is aminotrimethylenephosphonic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, divinyl three Five methylenephosphonic acid of amine, 2- hydroxyphosphonoacetic acid, double 1,6 hexamethylene triamine, five methylenephosphonic acids, hexapotassium, second two It is one or more in four methylenephosphonic acid of amine and polyamino polyether base methylenephosphonic acid;
The fluoride is one of ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, trihydroxyethyl ammonium fluoride and hydrofluoric acid or a variety of;
The organic solvent is ether solvent and/or ketones solvent;
The corrosion inhibiter is one of 1,2-diaminocyclohexane tetraacetic acid, iminodiacetic acid, urea and ethylenediamine tetra-acetic acid or more Kind;
The organic amine be one of isopropanolamine, triethanolamine, hexa and pentamethyl-diethylenetriamine or It is a variety of;
The mass fraction of the organic amine is 5%-40%;
The mass fraction of the dispersing agent is 2.5%-3.5%;
The mass fraction of the corrosion inhibiter is 0.5%-10%.
2. the preparation method of cleaning solution as described in claim 1, which is characterized in that
The mass fraction of the fluoride is 0.05%-20%;
And/or the mass fraction of the organic solvent is 10%-65%.
3. the preparation method of cleaning solution as claimed in claim 2, which is characterized in that
The mass fraction of the fluoride is 2.5%-15%;
And/or the mass fraction of the organic solvent is 30%-50%;
And/or the mass fraction of the corrosion inhibiter is 0.5%-5%;
And/or the mass fraction of the organic amine is 13%-25%.
4. the preparation method of cleaning solution as claimed in claim 3, which is characterized in that
The mass fraction of the fluoride is 3-10%;
And/or the mass fraction of the organic solvent is 35-45%;
And/or the mass fraction of the corrosion inhibiter is 1%-3%;
And/or the mass fraction of the organic amine is 15%-20%.
5. the preparation method of cleaning solution as described in claim 1, which is characterized in that
The water is one of deionized water, distilled water, pure water and ultrapure water or a variety of.
6. the preparation method of cleaning solution as claimed in claim 5, which is characterized in that
The ether solvent be propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, glycol monomethyl ether, One of ethylene glycol monoethyl ether and ethylene glycol diethyl ether are a variety of;
And/or the ketones solvent is one of acetone, methyl ethyl ketone, imidazolidinone, pyrrolidones and imidazolone or more Kind.
7. the preparation method of cleaning solution as claimed in claim 6, which is characterized in that
The imidazolidinone is 1,3- dimethyl -2- imidazolidinone;
And/or the pyrrolidones is N-Methyl pyrrolidone and/or hydroxyethyl-pyrrolidone;
And/or the imidazolone is 1,3-Dimethyl-2-imidazolidinone.
8. such as the preparation method of the described in any item cleaning solutions of claim 1-7, which is characterized in that the raw material components are by dividing Powder, fluoride, organic solvent, corrosion inhibiter, organic amine and water composition;Wherein, the dispersing agent is organic phosphine dispersing agent.
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