JPH09296200A - Composition of hydroxylamine-gall compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject composition for removing residual materials of a polymer material, an organic material, an organic metal and a metal oxide from a substrate, containing a hydroxylamine compound, an aminoalcohol compound miscible with the hydroxylamine compound and a gall compound.

SOLUTION: This composition contains (A) hydroxylamine, (B) at least one aminoalcohol compound miscible with the component A and (C) a gall compound, preferably represented by the formula (R is H, a 1-10C alkyl or an aryl; X is H, a halogen or a 1-5C alkyl). The component B is preferably a monoamine, diamine or triamine having a 1-5C alcohol group, e.g. an aminoalcohol of the formula R₁R₂-N-CH₂-CH₂-O-R₃(R₁ and R₂ are each independently H, CH₃, CH₃CH₂ or CH₂CH₂OH; R₃ is CH₂CH₂OH). Furthermore, the composition contains preferably about 10-70wt.% component A, about 30-60wt.% component B and about 5-15wt.% component C and the balance of water, etc.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to stripping and cleaning compositions and methods for removing polymeric materials and organic, organometallic and metal oxide residues from substrates. More particularly, it relates to such compositions and methods for removing polymers such as photoresists and polyimides, and the like, and etching residues after plasma etching steps in integrated circuit fabrication and similar processes. In particular, it relates to such compositions and methods that are effective in removing the above-mentioned materials when avoiding substantial corrosion of metal layers used in integrated circuits containing titanium layers.

[0002]

BACKGROUND OF THE INVENTION As the fabrication of integrated circuits becomes more complex and the dimensions of circuit elements fabricated on silicon or other semiconductor wafers become smaller, photoresists or other polymeric materials and formation from such materials. There is a need for continuous improvement in the technology used to remove the residue that is left behind. Photoresists such as polyimide or other polymeric materials are often needed for ion implantation, plasma etching, reactive ion etching, or ion milling during the fabrication process to define the pattern in the substrate. In addition, oxygen plasma oxidation is often used to remove photoresist or other polymeric materials after their use during the fabrication process. As a result of such high energy processes, on the sidewalls of the structures formed in the fabrication process,
Curing of the photoresist and formation of organometallics and other residues typically occur.

Aluminum, aluminum / silicon / copper,
Various metals and other layers including titanium, titanium nitride, titanium / tungsten, tungsten, silicon oxide, and polycrystalline silicon are commonly used in the fabrication of integrated circuits. The use of such different layers causes the formation of different organometallic residues in high energy processes. The stopping and cleaning compositions, in addition to being effective in removing photoresist or other polymeric materials, or residues, will not compromise the various metallurgy used in the fabrication of integrated circuits.

[0004] The assignee of the present application, EKC Technology (EKC), disclosed in the previous application and issued patents noted above.
Technology. Hydroxylamine-based compositions commercially available from Inc) have proven to be highly effective photoresist and etch residue removers in the integrated circuit industry. Substrates compatible with chemicals used in wet processes as a result of continued efforts to reduce critical dimensions in the integrated circuit industry, such as the fabrication of submicron sized devices. And are very large scale integration (VLS
In I) and ultra large scale integration (ULSI) manufacturing processes, it is becoming increasingly important to obtain acceptable products. Such etching residue compositions generally consist of the etched substrate, the underlying substrate, the photoresist, and the etching gas. The substrate compatibility of wafers with wet chemistries such as hydroxylamine compositions is often quite different in each fabrication step,
It relies heavily on the processing steps of polysilicon, multilevel interconnection dielectric layers, and metallization in thin film deposition, etching, and wafer post-etching processes.

In certain circumstances, catechol (1,2
Hydroxylamine compositions, such as those containing (dihydroxybenzene), corrode certain metal substrates at elevated temperatures, eg, above 65 ° C., such as substrates containing titanium metal layers or substrates containing aluminum layers. . Titanium has become more widely used in semiconductor manufacturing processes. Titanium is used both as a barrier layer to prevent electromigration of certain atoms and as an anti-reflector layer on top of other metals. Catechol is applicable to Federal regulations (SE).
It is considered to be a dangerous material under RA Title III)). In pursuing the introduction of more effective and less toxic wet chemicals for the semiconductor industry, a study was conducted to find a replacement for a suitable catechol in the hydroxylamine composition.

[0006]

Accordingly, it is an object of the present invention to provide improved hydroxylamine-based compositions and methods using the above-described compositions that meet the current semiconductor fabrication needs encountered. .

Yet another object of the present invention is to remove photoresist and other polymeric materials and residues from wafers and other substrates containing one or more titanium metal layers without essentially attacking the titanium layers. It is to provide such a composition and method suitable for removal.

Yet another object of the present invention is to provide a composition and method as described above containing more health and environmentally friendly chemicals.

[0009]

The accomplishment of the foregoing and related ends can be accomplished through the use of the hydroxylamine-gallate compound compositions disclosed herein and methods of making the same. The hydroxylamine-gallate compound composition according to the present invention comprises a hydroxylamine compound, at least one alcohol amine compound miscible with the hydroxylamine compound, and a gallic compound. According to the present invention, a method for removing photoresist and other polymeric materials or residues from a substrate is provided with the substrate at a time and temperature sufficient to remove the photoresist, other polymeric materials, or residues from the substrate. , A composition containing a hydroxylamine compound, an alcoholamine compound miscible with the hydroxylamine compound, and a gallic compound.

In the practice of the present invention, the substitution of about the same amount of gallate compound for catechol is at least about 3 times less titanium corrosion than the composition containing catechol, for stripping and cleaning photoresist or for residue removal. A composition is provided. At the same time, gallic compound-containing compositions provide comparable performance as photoresist stripping and cleaning or residue removal compositions.

The attainment, advantages and features of the above and related objects of the present invention will be readily apparent to those skilled in the art by reference to the following more detailed description of the invention in conjunction with the drawings. .

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hydroxylamine suitable for use in the present invention has the structural formula H ₂ N--OH. Hydroxylamine, as its structure has often a characteristic of hydrazine i.e. H ₂ N-NH _2, and properties of hydrogen peroxide i.e. HO-OH, a characteristic which is located between . Hydroxylamine in its pure form is a colorless, deliquescent solid with a melting point of 33 ° C., which explodes on heating and decomposes slowly at ambient or room temperature to yield dinitrogen monoxide and nitrogen. Hydroxylamine is a product of Nissin Chemical
Al) and is commercially available as an aqueous solution in an amount of about 50% by weight. In order to improve the stability during storage, a drug stabilizer is added to the solution by Nissin Chemical. In practice, this commercially available form of hydroxylamine is used in the present invention, and the amount details refer to the commercially available form. Hydroxylamine is reported to the manufacturer as not compatible with titanium.

Alcohol amines suitable for use in the present invention are miscible with hydroxylamine and are preferably water soluble. In addition, the alcohol amines useful in the present invention preferably have a relatively high boiling point, such as 75 ° C or higher. Suitable alcohol amines are primary, secondary or tertiary amines, preferably monoamines, diamines or triamines, most preferably monoamines. The alcohol group in the alcohol amine preferably has 1 to 6 carbon atoms and can be based on straight-chain, branched or cyclic alcohols.

Preferred alcohol amines suitable for use in the present invention have the following chemical formula: R ₁ R ₂ --N--CH ₂ C
Has a H ₂ -O-R _3, wherein R ₁ and R ₂ are independently in each _{case, H, CH 3, CH 3} CH 2, or a CH ₂ CH ₂ OH, R ₃ is It is CH ₂ CH ₂ OH.

Examples of suitable alcohol amines are monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, diisopropanolamine, 2-amino-1.
-Propanol, 3-amino-1-propanol, isobutanolamine, 2-amino-2-ethoxyethanol (diglycolamine), 2-amino-2-ethoxy-propanol, and 1-hydroxy-2-aminobenzene. .

Gallic compounds suitable for use in the present invention have the following structural formula:

[0017]

Embedded image

In the above structural formula, R is hydrogen, or an alkyl group or allyl group containing 1 to 10 carbon atoms, and X is hydrogen, halogen, or an alkyl group containing 1 to 5 carbon atoms. is there. Preferred gallic compounds are gallic acid, eg R and X are hydrogen or propyl gallate, eg R are propyl and X is hydrogen.

Preferably, the composition contains at least about 5% by weight hydroxylamine, at least about 10% by weight at least one alcohol amine, and about 2 to about 30% by weight gallic acid compound. The balance of the composition consists of water, preferably highly pure deionized water, or other suitable polar solvent. The solvents may be used alone or as a mixture. The composition is preferably
About 5 to about 80% by weight of hydroxylamine and about 10
It comprises 80% by weight of at least one alcohol amine and about 5 to about 30% by weight of the gallic compound, the balance of which is water or other suitable polar solvent.

Applicants do not intend to relate to any particular theory of action, but alcohol amines react in situ with gallic compounds to form either amide or ammonium phenolate salts. Examples of polar solvents suitable for the composition include, in addition to water, dimethyl sulfoxide, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl ether, propylene glycol, propylene glycol alkyl ether, dimethyl sulfoxide, N-substituted. Includes pyrrolidone, ethylenediamine, and ethylenetriamine. Additional polar solvents well known to those skilled in the art may also be used in the compositions of the present invention.

Although the stripping and cleaning composition of the present invention is effective in removing a wide range of positive photoresists, it is sensitized with novolac type binders or resins and O-naphthoquinone diazide sulfonic acid ester or amide sensitizers. It is particularly useful in removing photoresists that commonly consist of agents. Examples of commercially available photoresist compositions that effectively remove the stripping and cleaning composition of the present invention from a substrate are described in K. K. T. I. Photoresist 820, 825 (KTI photore
systems 820, 825; Philip A .; Hun
t Chemical Corp. ), Way coat H
PR104, HPR106, HPR204, and HPR
206 photoresist (Waycoat HPR104,
HPR106, HPR204, and HPR206pho
torelists; Shipley Compan
y, Inc. ), AZ-1300 series, AZ-14
00 series and AZ-2400 series photoresist (Tokyo Ohka Kogyo Co, Lt.
d), including photoresist OFPR-800.

In addition, the polyimide coating is about 40
The stripping and cleaning compositions of the present invention are effective in removing polyimide coatings from substrates even when subjected to high temperature curing, including curing performed at temperatures as low as 0 ° C. An example of a commercially available polyimide composition that the stripping and cleaning composition of the present invention effectively removes from a substrate is Ciba Kaiggy Proimide 293.
(Ciba GeigyPromide 293), Asahi G-6246-S (Asahi G-6246-S),
And DuPont PI2545 and PI2555 (DuPo
nt PI2545 and PI2555).

Examples of substrates where the stripping and cleaning composition of the present invention removes photoresist without attacking the substrate itself are aluminum, titanium, tungsten, titanium / tungsten / aluminum / silicon /
Includes metal substrates such as copper, and substrates such as silicon oxide, silicon nitride, and gallium / arsenide, and plastic substrates such as polycarbonate.

The stripping and cleaning composition of the present invention is also effective in removing the organometallic and metal oxides formed on the substrate of the etching equipment utilized. Examples of commercially available etching equipment are Lam Research, Tegal.
al), Electrotec (Electrotec)
h), Applied Materials (Applied Ma)
terials, Tokyo Electronics
ron), devices obtained from Hitachi, etc.

A method of removing resist or other material from a substrate using the stripping and cleaning composition of the present invention comprises the step of having the resist on the substrate for a time and at a temperature sufficient to remove the resist. To the stripping and cleaning composition of the present invention. The temperature and time are determined based on the particular material being removed from the substrate. Generally, the temperature will be about ambient temperature or room temperature to about 120 ° C.
The contact time is about 2 to 60 minutes.

A method of stripping and cleaning a substrate using the stripping and cleaning composition of the present invention is a method of stripping and cleaning a composition of the present invention for a time and at a temperature sufficient to remove residues. Contacting the substrate with the organometallic and metal oxide residues on the substrate. The substrate is typically immersed in the stripping and cleaning composition.
The time and temperature are determined based on the particular material being removed from the substrate. Generally, the temperature will range from about ambient or room temperature to about 120 ° C. and the contact time will be about 2-60 minutes.

In any case, the substrate may then be washed with a polar solvent such as isopropyl alcohol followed by deionized water.

[0028]

The present invention will be further described with reference to the following non-limiting examples. Examples of stripping and cleaning compositions according to the present invention suitable for removing resist from a substrate, or for removing resist or other organic residues from a substrate are set forth in Table 1 below. Compositions A and G
Is a comparative composition used to provide a frame of reference for the results obtained with the gallic compound-containing composition. Composition F is a conventional composition used for photoresist and residue removal in one of the Examples described below.

[0029]

[Table 1]

EXAMPLE 1 This example demonstrates that the substitution of gallic acid for catechol in the hydroxylamine stripping and cleaning composition is much weaker than the catechol-containing stripping and cleaning composition for titanium metallurgy on semiconductor wafers. It is shown to impart corrosiveness to the stripping and cleaning composition. The change in size of metallurgical films used in semiconductor manufacturing can be determined by measuring the change in sheet resistance using the following equation:

Equation: sheet resistance = resistivity / film thickness Prometrics Four Point Probe (Prome
standard thickness 35 determined by measuring sheet resistance using a Trix-FourPoint Probe)
Experiments were conducted with wafers having a sputtered titanium film of 00-4000 Angstroms. Sample wafers at 75 ° C for 30, 60, and 12
Compositions A, B, C, D, G listed in Table 1 for 0 minutes
And I.

1 to 4 are graphs showing the measurement results in a format in which the percentage of the remaining thickness is plotted against time. FIG. 1 is a comparison of compositions A and B (catechol vs. gallic acid in the monoethanolamine system). FIG. 2 is a comparison of compositions G and E (catechol vs gallic acid in the diglycolamine system). FIG. 3 shows compositions B and C
The effect of gallic acid concentration in the monoethanolamine system is shown in comparison with. FIG. 4 is a comparison of compositions C and D (monoethanolamine based gallic acid vs. isopropanolamine based gallic acid).

FIG. 1 shows that the corrosion of titanium obtained with a stripping and cleaning composition B containing gallic acid was comparable to that of a conventional strike containing catechol in the same hydroxylamine stripping and cleaning solution on the other hand. The reduction is clearly shown compared to the ripping and cleaning composition A. Example 2 Composition M was used to show that the present invention also prevents contamination of mobile ions from the wafer surface. Wafer samples were prepared for evaluation of mobile ion contamination as follows. TiN / Al
A metal film consisting of Si / TiN / Ti was sputtered on a boron tetraethyl orthosilicate (BTEOS) wafer. The wafer was then patterned with photoresist and metal film etched in a plasma etch system. The photoresist was removed by oxygen plasma ashing. 3 at 75 ° C with composition M
BTE by SIMS test before and after treatment for 0 minutes
Contamination on the OS surface was measured. Spray cleaner (Spr
All samples were washed with deionized water for 5 cycles in an ay liner). The sample was then dried with a nitrogen gun. Table 2 shows the results obtained with and without the treatment with composition M.

[0034]

[Table 2]

The results show that composition M is able to remove sodium from the wafer surface. Example 3 Via holes in the silicon oxide dielectric layer were etched through the holes in the photoresist pattern using standard silicon oxide plasma etching methods. The photoresist was removed by oxygen plasma ashing. FIG. 5 shows a scanning electron microscope (SE
Figure 3 shows a micrograph of the image of M) showing that there is a large amount of organometallic etch residue left on the substrate surface, especially around the via holes. Then, the substrate was treated at 70 ° C. for 30 minutes. FIG. 6, the resulting SEM picture, shows that composition B removed all organometallic residues.

Example 4 The 0.
A 6 micron size via hole was etched through the photoresist patterned hole using a standard silicon oxide plasma etching method. The photoresist was removed using oxygen plasma ashing. The SEM photographs of FIGS. 7 and 8 show that a large amount of etching residue is present in the via holes. The micrograph in Figure 9 shows 3 at 70 ° C.
After treatment with composition E for 0 minutes, composition E was shown to completely remove all residue. Composition F, a commercially available photoresist stripper containing N-ethylhydroxy-2-pyrrolidone, partially removed etching residues after treatment at 120 ° C. for 30 minutes, as shown in FIG. did.

Example 5 This example shows the working ability of a stripping and cleaning composition in which catechol was replaced with propyl gallate. Composition H was used in plasma oxygen etched via holes. The photoresist used as the mask for the via etch in this experiment was not removed by an oxygen plasma ashing step on several wafers to demonstrate that the stripping and cleaning composition can also remove the plasma etched photoresist. It was FIG.
Shows a via wafer having a photoresist layer after via etching. FIG. 12 shows the organic acid and oxide residues left on the wafer surface after oxygen plasma ashing. 13 and 14 show that after the composition H was exposed to the environment of plasma oxygen etching, it effectively removed the photoresist and after treatment for 30 minutes at 65 ° C., the organometallic and It shows that the oxygen residue was removed.

Example 6 This example demonstrates the different corrosiveness of composition G containing catechol and composition I containing gallic acid. TiN / AlSi / Ti / T
A sandwich metal thin film of iN / Ti metallurgy was patterned and etched with a plasma metal etcher. FIG. 15 shows that after removing the photoresist by oxygen plasma ashing, the organometallic residue remains on the metal wire surface. As shown in FIG. 16, after exposing the wafer to the composition G at 75 ° C. for 30 minutes, the titanium barrier layer (Ti / TiN / Ti) was cut off. Stripper composition I containing gallic acid under the same process conditions did not attack the barrier layer, as shown in FIG.

Example 7 This example further illustrates the reduction of corrosion of titanium barrier metal films by a stripping and cleaning composition containing gallic acid. W
The tests were performed on plasma metal etched wafers with / Ti metallurgy. The photoresist was removed by oxygen plasma ashing. 75 the wafer
Immerse in stripping and cleaning solution for 30 minutes at ° C. As shown in FIG. 18, the titanium barrier layer was severely laterally corroded by the composition G containing catechol. Stripping and cleaning composition I containing gallic acid did not impact any on the titanium film, as shown in FIG.

Example 8 This example shows that the added polar solvent can be added to the hydroxylamine / gallic acid stripping and cleaning composition without compromising the performance of the composition. 21 and 22 show 75
Figure 3 shows the results for plasma etched metal and via wafers treated in Composition J for 30 minutes at 0 ° C. Composition J removed all etching residues without corroding the titanium barrier metal layer.

Example 9 In this example, composition K, a hydroxylamine / gallic acid stripping and cleaning composition using isopropanolamine as the alcoholamine, was used without corroding the titanium barrier metal layer. Prove that all etching residues have been removed. 23, 24, and 25 show the results of plasma etched metal and via wafers treated in Composition K at 75 ° C. for 30 minutes.

Example 10 This example shows that a hydroxylamine stripping and cleaning composition containing gallic acid can remove post-etch photoresist residues from a polysilicon substrate. Silicon wafers having an etched polysilicon layer having a thickness of about 400 nm were made into layers 30, 45, and 6
Immersion in composition I for 0 minutes at 95 ° C. The wafer was then dried with a dry nitrogen gun. After that, Hitachi S-
Inspected by 4500FE Scanning Electron Microscope (SEM) to evaluate the ability of composition B to remove etching residues.

SEM photographs of untreated and treated wafers are shown in FIGS. 26, 27, 28, 29 and 30. Most of the residue is on the sidewalls of the polysilicon lines as shown in FIGS. After immersion in Composition I for 30 and 45 minutes, most of the residues are completely removed as shown in FIGS. 28 and 29. The residue was completely removed after immersion of Composition I for 60 minutes as shown in Figure 30, which is an acceptable manufacturing condition for wafer preparation.

Example 11 This example shows that gallic acid works equally well on mixtures of alcohol amines. Composition K is a solution containing monoethanolamine and diglycolamine. 31 and 32
Show that after treating composition K at 75 ° C. for 30 minutes and 60 minutes, it is effective in removing the residue without attacking the titanium barrier metal layer in the metal and via etch wafer.

(Example 12) Composition L in which the alcohol amine is isopropanol amine as shown in FIG.
Effectively removed all etching residues after metal and via etching without attacking the Ti barrier metal layer when used in a treatment at 75 ° C. for 60 minutes.
FIG. 34 shows the effectiveness of removing via etch residue from the via holes.

In summary, the above examples show that Compositions B-E and H-L have no adverse effect on the substrate.
It has the ability to remove photoresist and etch residues on various wafers such as metal, via, and polysilicon wafers. These compositions compare to compositions A, F and G, especially Ti and A at high temperatures.
l shows better performance in terms of substrate compatibility with metal films. Compositions B-E and HL are compositions A and G
Unlike the Emergency Planning and Community Light To Know Act of 1986, it contains no substances relating to the reporting requirements of Section 313 and 40 CFR 372.

It is provided that new compositions and methods are provided which are able to achieve the stated objects of the invention.
It will be readily apparent to those skilled in the art. The improved hydroxylamine-based compositions and methods using the above-described compositions of the present invention meet the current semiconductor fabrication requirements encountered. The present compositions and methods are compatible with removing photoresist and other polymeric materials, and residues from wafers and other substrates containing one or more titanium metal layers without essentially attacking the titanium layers described above. . The compositions and methods do not include or use any materials for reporting requirements.

Various changes in form and detail of the invention, as shown and described, can be made.
It will be further apparent to those skilled in the art. It is intended that such changes be included within the spirit and scope of the appended claims.

[Brief description of drawings]

1 compares compositions A and B in titanium thickness measurements after treatment with other stripping and cleaning and residue removal compositions as compared to stripping and cleaning and residue removal compositions according to the present invention. 7 is a graph showing a result regarding.

FIG. 2: Comparison of compositions G and I in titanium thickness measurements after treatment with other stripping and cleaning and residue removal compositions compared to stripping and cleaning and residue removal compositions according to the invention. 7 is a graph showing a result regarding.

FIG. 3 is a comparison of compositions C and B in titanium thickness measurements after treatment with other stripping and cleaning and residue removal compositions compared to stripping and cleaning and residue removal compositions according to the present invention. 7 is a graph showing a result regarding.

FIG. 4 Compositions C and D in titanium thickness measurements after treatment with other stripping and cleaning and residue removal compositions compared to stripping and cleaning and residue removal compositions according to the invention. 7 is a graph showing a result regarding.

FIG. 5 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 6 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 7 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 8 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 9 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 10 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 11 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 12 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 13 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 14 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 15 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 16 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 17 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 18 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 19 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 20 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 21 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 22 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 23 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 24 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 25 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 26 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 27 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 28 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 29 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 30 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 31 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 32 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 33 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

FIG. 34 is a scanning electron microscope (SEM) photograph showing comparative results achieved using the compositions and methods of the present invention.

Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01L 21/3065 H01L 21/30 572B 21/304 341 21/302 N 21/306 21/306 S // (C11D 7/50 7:32 7:28)

Claims (36)

[Claims] 1. A composition for removing photoresist or other polymeric material or residue from a substrate, which comprises hydroxylamine, at least one alcoholamine compound miscible with the hydroxylamine, and a gallic compound. A composition comprising: 2. The gallic compound has the following general formula: (In the formula, R is hydrogen or an alkyl group or an aryl group having 1 to 10 carbon atoms, and X is hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms.) The composition according to claim 1, characterized in that it is represented. 3. The at least one alcohol amine has an alcohol group having 1 to 5 carbon atoms,
The composition according to claim 2, wherein the composition is a monoamine, a diamine, or a triamine. 4. The at least one alcohol amine has the following formula: R ₁ R ₂ —N—CH ₂ CH ₂ —O—R ₃ , wherein R ₁ and R ₂ are in each case independent. H, CH ₃ , CH ₃ CH ₂ , or CH ₂ CH ₂ OH
And R ₃ is CH ₂ CH ₂ OH. 5. The composition comprises at least about 5% by weight of the hydroxylamine, at least about 10% by weight of the at least one alcohol amine, and from about 2 to about 3%.
A composition according to claim 1, characterized in that it comprises 0% by weight of the gallic compound and that all the rest of the composition essentially comprises polar solvents. 6. The composition comprises from about 10 to about 70% by weight of hydroxylamine, from about 30 to about 60% by weight of the at least one alcohol amine, and from about 5 to about 15% by weight of the gallic compound. The composition according to claim 5, comprising: 7. The composition of claim 5, wherein the polar solvent comprises water or dimethylsulfoxide. 8. The composition of claim 5, wherein the at least one alcohol amine comprises at least two alcohol amines. 9. The composition of claim 8 wherein one of the at least two alcohol amines is monoethanolamine. 10. The composition of claim 8, wherein one of the at least two alcohol amines is diglycol amine. 11. A method for removing photoresist or other polymeric material or residue from a substrate, the time being sufficient to remove the photoresist, other polymeric material, or residue from the substrate. And contacting the hydroxylamine compound, an alcoholamine compound miscible with the hydroxylamine compound, and a gallic compound at a temperature and at a temperature. 12. The time period is about 2 minutes to about 60 minutes,
The method of claim 11, wherein the temperature is about 20 ° C to about 110 ° C. 13. The gallic compound has the following general formula: (In the formula, R is hydrogen or an alkyl group or an aryl group having 1 to 10 carbon atoms, and X is hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms.) The method according to claim 11, characterized in that it is represented. 14. The method according to claim 13, wherein the at least one alcohol amine is a monoamine, diamine, or triamine having an alcohol group having 1 to 5 carbon atoms. 15. The at least one alcohol amine has the following formula: R ₁ R ₂ —N—CH ₂ CH ₂ —O—R ₃ , where R ₁ and R ₂ are in each case independent. And H, CH ₃ , CH ₃ CH ₂ , or CH ₂ CH ₂ O
Is H, A method according to claim 14 R ₃ is CH ₂ CH ₂ OH. 16. The substrate is coated with at least about 5% by weight of the hydroxylamine, at least about 10% by weight of the at least one alcohol amine, and from about 2 to about 3%.
12. The method of claim 11, wherein the composition comprises 0% by weight of the gallic compound, the remainder of the composition being contacted essentially with the polar solvent. 17. The composition comprises from about 10% to about 70% by weight.
17. The method of claim 16, comprising about 30 to about 60% by weight of the at least one alcohol amine and about 5 to about 15% by weight of the gallic compound. 18. The method of claim 16, wherein the polar solvent comprises water or dimethylsulfoxide. 19. The method of claim 16, wherein the at least one alcohol amine comprises at least two alcohol amines. 20. The method of claim 19, wherein one of the at least two alcohol amines is monoethanolamine. 21. The method of claim 19, wherein one of the at least two alcohol amines is diglycol amine. 22. The method of claim 11, further comprising cleaning the substrate with a cleaning polar solvent. 23. The method of claim 22, wherein the wash polar solvent is isopropyl alcohol. 24. A composition for removing photoresist or other polymeric material or residue from a substrate, comprising:
A composition comprising a reaction product between hydroxylamine, at least one alcoholamine compound miscible with the hydroxylamine, and a gallic compound. 25. The composition according to claim 24, wherein the reaction product is a reaction product of at least one alcohol amine compound miscible with the hydroxylamine and a gallic compound. 26. The reaction product according to claim 2, wherein the reaction product is an amide salt or an ammonium phenolate salt.
6. The composition according to 5. 27. The gallic compound has the following general formula: (In the formula, R is hydrogen or an alkyl group or an aryl group having 1 to 10 carbon atoms, and X is hydrogen, halogen, or an alkyl group having 1 to 5 carbon atoms.) 25. The composition according to claim 24, characterized in that it is represented. 28. The composition of claim 27, wherein the at least one alcohol amine is a monoamine, diamine, or triamine having an alcohol group having 1 to 5 carbon atoms. 29. The at least one alcoholic amine
Has the following formula: R₁R_Two-N-CH_TwoCH_Two-OR_ThreeTo
Have, where R₁And R_TwoIs independent in each case
And then H, CH_Three, CH_ThreeCH_TwoOr CH_TwoCH_TwoO
H and R _ThreeIs CH_TwoCH_Two28. It is OH.
A composition as described. 30. The compositional mixture comprises at least about 5% by weight of the hydroxylamine, at least about 10% by weight of the at least one alcohol amine, and about 2 to about 30% by weight of the gallic compound. 25. The composition of claim 24, comprising the reaction product formed, wherein the remainder of the mixture consists essentially of polar solvents. 31. The mixture forming the composition is about 10
About 70% by weight of hydroxylamine and about 30 to about 60
Wt% of said at least one alcohol amine and about 5
31. The composition of claim 30, wherein the reaction product is formed from about 15% by weight of the gallic compound. 32. The composition according to claim 30, wherein the polar solvent contains water or dimethyl sulfoxide. 33. The composition of claim 30, wherein the at least one alcohol amine comprises at least two alcohol amines. 34. The composition of claim 33, wherein one of the at least two alcohol amines is monoethanolamine. 35. The composition of claim 33, wherein one of the at least two alcohol amines is diglycol amine. 36. A method for removing photoresist or other polymeric material or residue from a substrate, comprising contacting the substrate with a composition according to any one of claims 24-35. A method comprising.