USO0953673OB2

(12) United States Patent (10) Patent No.: US 9,536,730 B2 Lee et al. (45) Date of Patent: Jan. 3, 2017

(54) CLEANING FORMULATIONS 7/3209 (2013.01): CIID 7/3218 (2013.01); CIID 7/3281 (2013.01); CIID 7/5013 (71) Applicant: AIR PRODUCTS AND CHEMICALS (2013.01); CIID 7/5022 (2013.01); G03F INC. Allentown, PA (US) 7/425 (2013.01); G03F 7/426 (2013.01) (58) Field of Classification Search (72) Inventors: Yi Chia Lee, Dansheui (TW); CPC ...... C11D 11/0047; C11D 7/50 Madhukar Bhaskara Rao, Fogelsville, See application file for complete search history. PA (US); Gautam Banerjee, Latham, NY (US); Wen Dar Liu, Chupei (TW); Aiping Wu, Macungie, PA (US); Seiji (56) References Cited Inaoka, Midland, MI (US) U.S. PATENT DOCUMENTS Assignee: AIR PRODUCTS AND (73) 5,279,771 A 1/1994 Lee CHEMICALS, INC., Allentown, PA 5,417,877 A 5, 1995 Ward (US) 5,746,837 A 5/1998 Becket al. 6,117,783 A 9, 2000 Small et al. (*) Notice: Subject to any disclaimer, the term of this 6,248,704 B1 6/2001 Small et al. patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by 392 days. FOREIGN PATENT DOCUMENTS (21) Appl. No.: 14/010,748 EP O 647 884 A1 4f1995 (22) Filed: Aug. 27, 2013 EP 1736534 A1 12/2006 (Continued) (65) Prior Publication Data Primary Examiner — Gregory Webb US 2014/O109931 A1 Apr. 24, 2014 (74) Attorney, Agent, or Firm — Anne B. Kiernan; Joseph Related U.S. Application Data D. Rossi (60) Provisional application No. 61/717,152, filed on Oct. 23, 2012, provisional application No. 61/817,134, (57) ABSTRACT filed on Apr. 29, 2013. A composition and method for removing copper-containing post-etch and/or post-ash residue from patterned microelec (51) Int. C. tronic devices is described. The removal composition CLID 7/50 (2006.01) includes water, a water-miscible organic solvent, an amine HOIL 2L/02 (2006.01) compound, an organic acid, and a fluoride ion source. The CLID 7/10 (2006.01) compositions effectively remove the copper-containing CLID 7/26 (2006.01) post-etch residue from the microelectronic device without CLID 7/32 (2006.01) damaging exposed low-k dielectric and metal interconnect GO3F 7/42 (2006.01) materials. (52) U.S. C. CPC ...... HOIL 21/02052 (2013.01): CIID 7/10 (2013.01); CIID 7/265 (2013.01): CIID 21 Claims, 1 Drawing Sheet

Before Clean 950 (25C, 1min)

Sidewal

(a) (c)

Top surface

(d) US 9,536,730 B2 Page 2

(56) References Cited 2007/0078073 A1 4/2007 Auger 2007/0179072 A1* 8, 2007 Rao ...... C11D 7/08 U.S. PATENT DOCUMENTS 51Of 175 2008/O139436 A1* 6/2008 Reid ...... C11D 3/044 6,326,130 B1 12/2001 Schwartzkopf et al. 510, 176 6,749,998 B2 6/2004 Schwartzkopfet al. 2008. O169004 A1* 7, 2008 Wu ...... C11D 7/08 6,755,989 B2 6/2004 Wojtczak et al. 134.2 6,787.293 B2 9/2004 Oowada et al. 7,250,391 B2 7/2007 Kanno et al. 2008/0242574 A1* 10, 2008 Rath ...... Goal: 7,399,365 B2 7/2008 Aoyama et al. 7,479,474 B2 1/2009 Cernat et al. 2009/0032766 A1* 2/2009 Rajaratnam ...... HOL 21,31111 7,700,533 B2 4/2010 Egbe et al. 252/79.1 7,718,591 B2 5, 2010 HSu 2009.0099051 A1 4/2009 Aoyama et al. 7,723,280 B2 5/2010 Brainard et al. 2009, O163396 A1* 6, 2009 HSu ...... C11D 3.3947 8,003,587 B2 * 8/2011 Lee ...... GO3F 7/425 510, 176 134/13 2009/0203566 A1* 8, 2009 Lee ...... GO3F 7/425 8,062,429 B2 * 1 1/2011 Lee ...... C11D 7.3263 51Of 175 ck 134/13 2009,0301996 A1 12/2009 Visintin et al. 8,951,948 B2* 2/2015 Rath ...... C11D 4. 2010/0035785 A1 2/2010 Wojtczak et al. 2001/0050350 Al 12/2001 Wojtczak et al. 2010.0043823 A1 ck 2/2010 Lee ...... CID, 2003/0078173 A1 4/2003 Wojtczak et al. 2003/O130149 A1* 7/2003 Zhou ...... C11D 7,3218 2010.0152086 Al 6 2010 Wu et al. 510, 176 2010, 0163788 A1 7/2010 Visintin et al. 2003/0181342 A1* 9/2003 Seijo ...... C11D 7.265 2011/0117751 A1 5, 2011 Sonthalia et al. 51Of 175 2012/0048295 A1 3/2012 Du ...... C11D 7/3245 2004, OO18949 A1 1/2004 Lee 134/3 2004/0038840 A1 2/2004 Lee ...... C11D 3,0073 510,202 FOREIGN PATENT DOCUMENTS 2004/0171503 A1 9, 2004 Rowto et al. 2004/O220065 A1 11, 2004 HSu EP 1813667 A1 8, 2007 2005, OO14667 A1 1/2005 Aoyama et al. EP 2500407 A1 9, 2012 2005/0090416 A1* 4/2005 Lee ...... C11D 3A30 JP 2005522O27 7/2005 51Of 175 JP 2005528660 9, 2005 2005/0187118 A1* 8/2005 Haraguchi ...... C11D 7/10 JP 2005532691 10/2005 51Of 175 JP 2008198994 8, 2006 2005/0215446 A1 9/2005 Wojtczak et al. JP 2008277718 11/2008 2006/0016785 A1 1/2006 Egbe et al. JP 2010147476 T 2010 2006/0178282 A1 8/2006 Suyama et al. WO 2006110645 A2 10, 2006 2006/0237392 A1 10/2006 Auger et al. WO 2006129549 12/2006 2006/0270573 A1 11/2006 Ikemoto et al. WO 2009073588 A1 6, 2009 2006/0293208 A1* 12/2006 Egbe ...... C11D 7.3263 510.407 * cited by examiner U.S. Patent Jan. 3, 2017 US 9,536,730 B2

3 s ss 3. CO S. ar US 9,536,730 B2 1. 2 CLEANING FORMULATIONS interconnect wiring, reactive ion etching (RIE) is used to produce vias through the interlayer dielectric to provide CROSS-REFERENCE TO RELATED contact between one level of silicon, silicide or metal wiring APPLICATIONS to the next level of wiring. These vias typically expose, Al, AlCu, Cu, Ti, TiN, Ta, TaN, silicon or a silicide such as, for This nonprovisional application claims the benefit of U.S. example, a silicide of tungsten, titanium or cobalt. The RIE Application No. 61/717,152, filed on Oct. 23, 2012, and U.S. process, for example, leaves a residue on the involved Application No. 61/817,134, filed on Apr. 29, 2013, both Substrate comprising a complex mixture that may include, provisional applications having the same title as the present for example, re-sputtered oxide material, polymeric material application. U.S. Application Nos. 61/717,152 and 61/817, 10 derived from the etch gas, and organic material from the 134 are hereby incorporated by reference in their entireties. resist used to delineate the vias. Additionally, following the termination of the etching BACKGROUND OF THE INVENTION step, the photoresist and etch residues must be removed from the protected area of the wafer so that the final finishing The present invention relates to cleaning compositions 15 operation can take place. This can be accomplished in a that can be used for a variety of applications including, for plasma “ashing step by the use of Suitable plasma ashing example, removing unwanted resist films, post-etch, and gases. This typically occurs at high temperatures, for post-ash residue on a semiconductor Substrate. In particular, example, above 200° C. Ashing converts most of the organic the present invention relates to cleaning compositions useful residues to volatile species, but leaves behind on the sub for the removal of residue, preferably copper-containing strate a predominantly inorganic residue. Such residue typi post-etch and/or post-ash residue, from the Surface of Sub cally remains not only on the surface of the substrate, but strates, preferably microelectronic devices, and methods of also on the inside walls of Vias that may be present. As a using said compositions for removal of same. result, ash-treated Substrates are often treated with a cleaning The background of the present invention will be described composition typically referred to as a “liquid stripping in connection with its use in cleaning applications involving 25 composition' to remove the highly adherent residue from the manufacture of integrated circuits. It should be under the Substrate. Finding a suitable cleaning composition for stood, however, that the use of the present invention has removal of this residue without adversely affecting, e.g., wider applicability as described hereinafter. corroding, dissolving or dulling, the metal circuitry has also In the manufacture of integrated circuits, it is sometimes proven problematic. Failure to completely remove or neu necessary to etch openings or other geometries in a thin film 30 tralize the residue can result in discontinuances in the deposited or grown on the Surface of silicon, gallium circuitry wiring and undesirable increases in electrical resis arsenide, glass, or other substrate located on an in-process tance. integrated circuit wafer. Present methods for etching Such a Cleaning of post-etch residues remains a critical process film require that the film be exposed to a chemical etching step for any low-k dielectric material to Succeed. As the agent to remove portions of the film. The particular etching 35 dielectric constant of the low-k material pushes below 2.4. agent used to remove the portions of the film depends upon the chemical and mechanical sensitivity increases (e.g., the nature of the film. In the case of an oxide film, for chemical strength decreases, etc.), thereby requiring shorter example, the etching agent may be hydrofluoric acid. In the process times and/or less aggressive chemistries. Unfortu case of a polysilicon film, it will typically be hydrofluoric nately, shorter process times generally translates to more acid or a mixture of nitric acid and acetic acid. 40 aggressive chemistries which can have a detrimental effect In order to assure that only desired portions of the film are on the low-k dielectric material, as well as other stack removed, a photolithography process is used, through which materials (e.g., copper, etch stop, etc.). Thus, improved a pattern in a computer drafted photo mask is transferred to cleaning chemistries with very high selectivity are desired. the surface of the film. The mask serves to identify the areas Prior art stripping compositions include, for example: of the film which are to be selectively removed. This pattern 45 U.S. Pat. No. 7,399,356 (Aoyama), U.S. Pat. No. 6,755,989 is formed with a photoresist material, which is a light (Wojtczak), U.S. Pat. No. 7,250,391 (Kanno), U.S. Pat. No. sensitive material spun onto the in-process integrated circuit 7,723,280 (Brainard), U.S. patent application Publication wafer in a thin film and exposed to high intensity radiation No. 2006/0016785 (Egbe); U.S. patent application Publica projected through the photo mask. The exposed or unex tion No. 2006/0178282 (Suyama), U.S. patent application posed photoresist material, depending on its composition, is 50 Publication No. 2006/0237392 (Auger), U.S. patent appli typically dissolved with developers, leaving a pattern which cation Publication No. 2006/0270573 (Ikemoto), U.S. patent allows etching to take place in the selected areas, while application Publication No. 2007/0078073 (Auger), and preventing etching in other areas. Positive-type resists, for U.S. patent application Publication No. 2009/0301996 (Vis example, have been extensively used as masking materials intin). Such prior art stripping compositions for removing to delineate patterns on a Substrate that, when etching 55 the etching residue suffer, however, from significant draw occurs, will become vias, trenches, contact holes, etc. backs. For example, their use tends to erode copper wire Increasingly, a dry etching process such as, for example, exposed on the bottoms of via holes. Moreover, where plasma etching, reactive ion etching, or ion milling is used porous interlayer low-k dielectrics are concerned, prior art to attack the photoresist-unprotected area of the substrate to stripping compositions either etch the porous interlayer form the Vias, trenches, contact holes, etc. As a result of the 60 dielectric materials or include components that adsorb into plasma etching process, photoresist, etching gas and etched the pores thus increasing the dielectric constant, k, of the material by-products are deposited as residues around or on dielectric materials, which may potentially negatively the sidewall of the etched openings on the substrate. impact the performance of the ultimate device. Such dry etching processes also typically render the resist With respect to U.S. Pat. No. 7,723,280, the solvent mask extremely difficult to remove. For example, in com 65 mixture includes an ether. Ether solvents, however, have the plex semiconductor devices such as advanced DRAMS and potential to damage the low-k layer. In particular, ether logic devices with multiple layers of back end lines of Solvents can penetrate the porous low-k dielectric layer US 9,536,730 B2 3 4 thereby increasing the layer's dielectric constant. Thus, ether compound selected from the group consisting of at least one Solvents can contaminate the porous low-k layer and alkanolamine and at least one aminopropylmorpholine. adversely affect its insulation ability. In addition, ether In yet another aspect, the present invention provides a Solvents can adversely affect and increase the copper etch composition useful for removing residue from a semicon rate. 5 ductor Substrate, the composition consisting essentially of Therefore, there is a need in the art for a cleaning a) from about 15% to about 50% by weight of water; b) from composition for back end of the line cleaning operations that about 10% to about 65% by weight of a water-miscible effectively cleans Substrates comprising porous interlayer organic solvent selected from the group consisting of pro dielectric layers, but does not significantly etch metals (e.g., pylene glycol, glycerol, dimethylacetamide, tetrahydrofuryl Cu, Al) or the porous low-k dielectrics, and that does not 10 alcohol, ethylene glycol, hexylene glycol, and mixtures significantly negatively impact the dielectric constant of the thereof; c) from about 1% to about 50% by weight of an porous low-k films. amine compound selected from the group consisting of a at least one alkanolamine and aminopropylmorpholine; d) BRIEF SUMMARY OF THE INVENTION 15 from about 1% to about 25% by weight of an organic acid; e) from about 0.01% to about 8% by weight of a fluoride ion The present invention satisfies this need by providing a source; and f) optionally, from about 0.1% to about 15% by composition useful for removing residue from a semicon weight of a Cu corrosion inhibitor selected from the group ductor Substrate, the composition comprising: a) from about consisting of benzotriazole, amino-benzotriazole, L-ascor 15% to about 50% by weight of water; b) from about 10% bic acid, gallic acid, Vanillin, diethylhydroxylamine, and to about 65% by weight of a water-miscible organic solvent; mixtures thereof. c) from about 1% to about 50% by weight of an amine In still yet another aspect, the present invention provides compound selected from the group consisting of a at least a composition useful for removing residue from a semicon one alkanolamine and aminopropylmorpholine; d) from ductor Substrate, the composition consisting essentially of about 1% to about 25% by weight of an organic acid; and e) 25 a) from about 15% to about 50% by weight of water; b) from from about 0.01% to about 8% by weight of a fluoride ion about 10% to about 65% by weight of a water-miscible Source, wherein the water-miscible organic solvent is not an organic solvent, wherein the water-miscible solvent is not an ether. ether; c) from about 1% to about 50% by weight of an amine In another aspect, the present invention provides a method compound selected from the group consisting of a at least for removing residue from a semiconductor Substrate, the 30 one alkanolamine and aminopropylmorpholine; d) from method comprising the steps of contacting the semiconduc about 1% to about 25% by weight of an organic acid; e) from tor substrate with a cleaning composition of claim 1, about 0.01% to about 8% by weight of a fluoride ion source: wherein the semiconductor Substrate comprises a porous and f) optionally, from about 0.1% to about 15% by weight dielectric material having a dielectric constant; rinsing the of a Cu corrosion inhibitor selected from the group consist cleaning composition from the semiconductor Substrate; and 35 ing of benzotriazole, amino-benzotriazole, L-ascorbic acid, drying the semiconductor substrate, wherein the dielectric gallic acid, Vanillin, diethylhydroxylamine, and mixtures constant of the porous dielectric material does not increase thereof. more than 0.50. In yet another aspect, the present invention provides a BRIEF DESCRIPTION OF THE DRAWING replenishment composition to be added to a cleaning com 40 position, said replenishment composition comprises a) from FIG. 1 shows (a) a side wall view and (b) a top surface about 20% to about 84% by weight of water; b) from about view including residue present on these Surfaces before 15% to about 40% by weight of a water-miscible organic cleaning and (c) the side wall view and (d) the top surface solvent, wherein the water-miscible solvent is not an ether, view after cleaning with cleaning composition 95O c) from about 1% to about 5% by weight of an amine 45 described in the examples. compound selected from the group consisting of at least one alkanolamine and at least one aminopropylmorpholine. DETAILED DESCRIPTION OF THE In yet another aspect, the present invention provides a INVENTION method for removing unwanted residues from a semicon ductor Substrate comprising the steps of contacting the 50 The present invention provides a composition whose semiconductor Substrate with a cleaning composition com components are present in amounts that effectively remove prising: a) from about 15% to about 50% by weight of water; residue from a substrate such as, for example, a semicon b) from about 10% to about 65% by weight of a water ductor Substrate. In applications concerning semiconductor miscible organic solvent, wherein the water-miscible solvent Substrates, such residues include, for example, photoresist is not an ether; c) from about 1% to about 20% by weight of 55 residues, ash residues, and etch residues such as, for an amine compound selected from the group consisting of at example, residues caused by reactive ion etching. Moreover, least one alkanolamine and at least one aminopropylmor a semiconductor Substrate also includes metal, silicon, sili pholine; d) from about 1% to about 25% by weight of at least cate and/or inter-level dielectric material such as deposited one organic acid; and e) from about 0.01% to about 8% by silicon oxides, which will also come into contact with the weight of a fluoride ion Source, wherein said contacting step 60 cleaning composition. Typical metals include copper, copper results in a loss of a portion of said cleaning composition; alloy, titanium, titanium nitride, tantalum, tantalum nitride, and adding a replenishment composition to said cleaning aluminum and/or aluminum alloy. The cleaning composition composition; said replenishment composition comprising: a) of the present invention is compatible with Such materials as from about 20% to about 84% by weight of water; b) from they exhibit a low metal and/or dielectric etch rate. In about 15% to about 40% by weight of a water-miscible 65 particular, compositions providing a copper etch rate of 4 organic solvent, wherein the water-miscible solvent is not an A/min or less, 3 A/min or less, or 2 A/min or less may be ether; c) from about 1% to about 5% by weight of an amine preferred. US 9,536,730 B2 5 6 Water Solvents can contaminate the porous low-k layer and The cleaning compositions of the present invention com adversely affect its insulation ability. In addition, ether prise water. In the present invention, water functions in Solvents can adversely affect and increase the copper etch various ways Such as, for example, to dissolve one or more rate. Accordingly, upon use, the compositions of the present Solid components of the composition, as a carrier of the 5 invention preferably do not increase the dielectric constant components, as an aid in the removal of the residue, as a of the low-k dielectric layer more than 0.50 and the Cuetch Viscosity modifier of the composition, and as a diluent. rate does not exceed 4 A/min. Preferably, the water employed in the cleaning composition Fluoride Ion is de-ionized (DI) water. The cleaning composition of the present invention also It is believed that, for most applications, water will 10 comprises one or more sources of fluoride ion. Fluoride ion comprise, for example, from about 15 to about 50% by wt. functions principally to assist in removing inorganic resi of water. Other embodiments of the present invention could dues from the substrate. Preferred compounds that provide comprise about 35 to about 50% by wt. of water. Other a fluoride ion Source according to the present invention are preferred embodiments of the present invention could com ammonium fluoride and quaternary ammonium fluorides prise from about 20 to about 40% by wt. of water. Yet other 15 Such as, for example, tetramethylammonium fluoride and preferred embodiments of the present invention could com tetrabutylammonium fluoride. A fluoride salt of an aliphatic prise from about 30 to about 35% by wt. of water. Still other primary, secondary or tertiary amine can be used. Examples preferred embodiments of the present invention could of Such amines are those having the formula: include water in an amount from about 32 to about 35% by weight or an amount effective to achieve the desired weight 20 percent of the other ingredients. wherein R', R, R and R individually represent H or a Water-Miscible Organic Solvent (C-C)alkyl group. Typically, the total number of carbon The cleaning composition of the present invention com atoms in the R. R. Rand R groups is 12 carbon atoms or prises one or more water-miscible organic solvent, wherein less. the water-miscible organic solvent is not an ether. In certain 25 In selecting the source of the fluoride ion, consideration embodiments of the present invention, metal lines on the should be given as to whether or not the source releases ions Substrate typically dictate whether a water-miscible organic that would adversely affect the surface being cleaned. For Solvent is used. For example, when aluminum lines are example, in cleaning semiconductor elements, the presence present on a substrate, the combination of water and fluoride of Sodium or calcium ions in the cleaning composition can ion will typically tend to etch the aluminum. In such 30 have an adverse effect on the surface of the element. In a embodiments, the use of water-miscible organic solvent can preferred embodiment, the fluoride ion source is ammonium significantly reduce, if not eliminate, etching of aluminum. fluoride. Examples of water-miscible organic solvents that can be It is believed that the amount of the compound used as the used are ethylene glycol, propylene glycol, 1,4-butanediol. Source of the fluoride ion in the cleaning composition will, hexylene glycol, dimethylsulfoxide, dimethyl acetamide, 35 for most applications, comprise, about 0.01 to about 8% by tetrahydrofurfuryl alcohol, glycerol, alcohols, sulfoxides, or weight or from about 0.01 to about 7% by weight of a mixtures thereof. Solution 40% ammonium fluoride, or Stoichiometric equiva Preferred water-miscible solvents include propylene gly lent thereof. Preferably, the compound comprises from about col, glycerol, dimethyl acetamide, tetrahydrofuryl alcohol, 0.02 to about 8% by weight, more preferably from about ethylene glycol, hexylene glycol, and mixtures thereof. 40 0.02 to about 6% by weight, still more preferably, about 1 to Dimethylacetamide, propylene glycol, glycerol, or combi about 8% by weight, and most preferably, from about nations thereof are most preferable. 0.025% to about 5% by weight of a solution of about 40% It is believed that, for most applications, the amount of ammonium fluoride. In some embodiments, the composition water-miscible organic solvent will comprise from about 10 will comprise about 0.01 to about 8% by weight or about to 65% by weight of the composition or from about 20 to 45 0.01 to about 7% by weight of a fluoride ion source, which 65% by weight of the composition. In some embodiments, may be provided by a 40% ammonium fluoride solution. the solvent comprises from about 35 to about 55% by weight Preferably, the compound comprises from about 0.02 to and, most especially, from about 45% to about 55% or from about 6% by weight of a fluoride ion source and, most about 48 to about 52% by weight of water-miscible organic preferably, from about 0.025% to about 5% or from about solvent by weight of the composition. In other preferred 50 0.04 to about 2.5% by weight of a fluoride ion source or from embodiments, the solvent comprises from about 10 to about about 0.05 to about 15% by weight of a solution of 40% 40% by weight, especially, from about 10 to about 35% by ammonium fluoride, most preferably, from about 0.0625% weight, and most especially, about 10 to about 30% by to about 12.5% or from about 0.1 to about 6.25% by weight weight. of a solution of 40% ammonium fluoride. It should be In the composition of the present invention, the water- 55 understood that the amount of fluoride ion used will typi miscible organic solvent functions primarily to dissolve cally depend, however, on the particular Substrate being organic residues. cleaned. For example, in certain cleaning applications, the The water-miscible solvent component of the composi amount of the fluoride ion can be relatively high when tions of the present invention does not include an ether cleaning Substrates that comprise dielectric materials that solvent. In other words, ethers are not employed as the 60 have a high resistance to fluoride etching. Conversely, in water-miscible solvent component of the compositions of other applications, the amount of fluoride ion should be the present invention. relatively low, for example, when cleaning Substrates that Without wishing to be bound by theory, it is believed that comprise dielectric materials that have a low resistance to ether solvents can damage the low-k layer. In particular, it is fluoride etching. believed that ether solvents can penetrate the porous low-k 65 pH/Buffer dielectric layer making it difficult to remove from the low-k The cleaning composition of the present invention pref layer and increasing the dielectric constant. Thus, ether erably includes a buffering agent to control the pH of the US 9,536,730 B2 7 8 composition, typically to within a range of from about 7 to also function to react with organic residue and chelate metals about 10 or from about 7 to about 9, with the preferred pH during the cleaning operation. range being between from about 8 to about 9 or from about Organic Acid 8.1 to about 10. There are various applications in which the The cleaning composition of the present invention also use of buffering is advantageous, indeed even quite impor comprises one or more organic acid, which functions as a pH tant because some applications exhibit a pH drift which can adjustor and, in some embodiments, as a buffer component. cause significant and undesirable variances in cleaning and Examples of organic acids may be aliphatic/aromatic Substrate etching. carboxylic acids, amino carboxylic acid, Sulfonic acids and Buffering agents for use in the present invention typically aminosulfonic acid. Exemplary carboxylic acids include, but 10 are not limited to, acetic acid, propionic acid, butyric acid, comprise a weak acid and a soluble salt containing the pentanoic acid, 3-methylbutanoic acid, hexanoic acid, hep conjugate base of the weak acid. For example, the buffering tanoic acid, octanoic acid, nonanoic acid, decanoic acid, agent can comprise a weak organic monoacid and its con dodecanoic acid, tridecanoic acid, tetradecanoic acid, pen jugate base such as, for example, acetic acid and ammonium tadecanoic acid, hexadecanoic acid, heptadecanoic acid, acetate. In other embodiments, the buffering agent may 15 octadecanoic acid, dodecanedioic acid, 2-methylheptanoic comprise an organic or inorganic base in combination with acid, 2-hexyldecanoic acid, oxalic acid, malonic acid, maleic an organic diacid. Examples of Suitable bases include: acid, fumaric acid, Succinic acid, itaconic acid, glutaric acid, ammonium hydroxide, amines, and quaternary ammonium adipic acid, malic acid, tartaric acid, acrylic acid, meth hydroxides. In semiconductor applications, it is preferred acrylic acid, citric acid, lactic acid, glycolic acid, ascorbic that the base not include metal ions, for example, sodium acid, anthranilic acid, gallic acid, benzoic acid, isophthalic and potassium, because they tend to contaminate the Sub acid, phthalic acid, trimellitic acid, pyromellitic acid, Sali strate. Preferred bases are the amine compounds described cylic acid, 2,4-dihydroxy benzoic acid and others. Exem herein and the preferred acids are the organic acides plary amino carboxylic acids include, but are not limited to, described herein. The amine compound and the organic acid glycine, dihydroxy ethyl glycine, alanine, valine, leucine, compound together function as a buffer when present in 25 asparagine, glutamine, aspartic acid, glutaric acid, lysine, amounts sufficient to form a buffer (i.e., when the molar ratio arginine, imino diacetic acid, nitrilo triacetic acid, ethylene of the acid to the base is from 1:1 to 1:10). diamine tetraacetic acid, 1.2-cyclohexadiamine tetraacetic Amine Compound acid, diethylene triamine pentaacetic acid, and others. The cleaning composition of the present invention com Exemplary Sulfonic/aminosulfonic acids include, but are not prises an amine compound, which may include (1) at least 30 limited to, benzyl Sulfonic acid, p-toluene Sulfonic acid, one alkanolamine; (2) at least one aminopropylmorpholine; 2-(N-morpholino)ethanesulfonic acid, N-(2-hydroxyethyl) or (3) both of at least one alkanolamine and at least one piperazine-N'-(ethanesulfonic acid), 3-N,N-bis(2-hydroxy aminopropylmorpholine. ethyl)amino-2-hydroxypropanesulfonic acid, 4-(N-mor In certain preferred embodiments of the present invention, pholino)butanesulfonic acid, N-(2-hydroxyethyl)piperazine the amine compound is at least one alkanolamine. Preferred 35 N'-(2-hydroxypropanesulfonic acid), N-(2-hydroxyethyl) alkanolamines include the lower alkanolamines which are piperazine-N'-(3-propanesulfonic acid), 2-(N- primary, secondary and tertiary having from 1 to 5 carbon cyclohexylamino)ethanesulfonic acid, and mixtures thereof. atoms. Examples of Such alkanolamines include N-methy In preferred embodiments, the organic acid is selected lethanolamine (NMEA), monoethanolamine (MEA), dietha from the group consisting of Oxalic acid, malonic acid, citric nolamine, mono-, di- and triisopropanolamine, 2-(2-amino 40 acid, acetic acid, imiodiacetic acid, lactic acid, para-toluene ethylamino)ethanol, 2-(2-aminoethoxy)ethanol, Sulfonic acid, gallic acid, ascorbic acid, and mixtures triethanolamine, N-ethyl ethanolamine, N,N-dimethyletha thereof. nolamine, N,N-diethyl ethanolamine, N-methyl dietha It is believed that the amount of the organic acid in the nolamine, N-ethyl diethanolamine, cyclohexylaminedietha composition will, for the most applications, comprise from nol, and mixtures thereof. 45 about 1% to about 25% by weight or from about 1% to about In preferred embodiments, the amine compound is an 15% by weight of the composition. Preferably, the organic alkanolamine selected from the group consisting of trietha acid comprises from about 2% to about 12% weight percent, nolamine (TEA), diethanolamine, N-methyl dietha preferably from about 6 to about 10%, and, more preferably, nolamine, diisopropanolamine, monoethanol amine, amino from about 3 to about 10% or from about 2 to about 5% by (ethoxy) ethanol (AEE), N-methyl ethanol amine, 50 weight of the composition. monoisopropanol amine, cyclohexylaminediethanol, and Corrosion Inhibitors mixtures thereof. The compositions of the present invention optionally In other preferred embodiments of the present invention, comprise at least one corrosion inhibitor. Corrosion inhibi the amine compound is aminopropylmorpholine. In Such tors serve to react with the substrate surface being cleaned, embodiments, an alkanolamine is typically not needed. 55 which may be a metal, particularly copper, or a nonmetal, to It is believed that the amount of the amine compound in passivate the Surface and prevent excessive etching during the composition will, for the most applications, comprise cleaning. In particular and without being bound to any from about 1% to about 50% by weight of the composition, particular theory, it is believed that the corrosion inhibitor specifically, about 8% to about 50% by weight of the forms a coating of an insoluble chelate compound on the composition, or more specifically, about 20% to about 50% 60 copper Surface, thus Suppressing contact between the pho by weight of the composition. In some embodiments, the toresist residue removal component and the metal thereby amine compound comprises from about 2% to about 15% preventing corrosion. weight percent and, more specifically, from about 3 to about Any corrosion inhibitor known in the art for similar 12% or about from 3 to about from 7% by weight of the applications, such as those disclosed in U.S. Pat. No. 5,417. composition. 65 877, which are incorporated herein by reference, may be In addition to functioning as the base component of a used. The use of a corrosion-inhibitor is particularly pre buffer, any amine compound not reacted with an acid may ferred when the composition is used to clean a metallic US 9,536,730 B2 10 Substrate. Examples of corrosion-inhibitors include aromatic raacetic acid, nitrotriacetic acid (NTA), citric acid, tartaric hydroxyl compounds, acetylenic alcohols, carboxyl group acid, gluconic acid, Saccharic acid, glyceric acid, oxalic acid, containing organic compounds and anhydrides thereof, and phthalic acid, maleic acid, mandelic acid, malonic acid, triazole compounds. lactic acid, Salicylic acid, catechol, gallic acid, propyl gal Exemplary aromatic hydroxyl compounds include phe- 5 late, pyrogallol, 8-hydroxyquinoline, and cysteine. Preferred nol, cresol, Xylenol, pyrocatechol, resorcinol, hydroquinone, chelating agents are aminocarboxylic acids Such as EDTA, pyrogallol, 1.2.4-benzenetriol, Salicyl alcohol, p-hydroxy CyDTA and aminophosphonic acids such as EDTMP. benzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphen It is believed that, for most applications, the chelating ethyl alcohol, p-aminophenol, m-aminophenol, diaminophe agent will be present in the composition in an amount of nol, amino resorcinol, p-hydroxybenzoic acid, 10 from about 0.1 wt.% to about 10 wt.%, preferably in an o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2-5-di amount of from about 0.5 wt.% to about 5 wt.% of the hydroxybenzoic acid, 3,4-dihydroxybenzoic acid and 3.5- composition. dihydroxybenzoic acid. Other commonly known components such as dyes, bio Exemplary acetylenic alcohols include 2-butyne-1,4-diol, cides etc. can be included in the cleaning composition in 3,5-dimethyl-1-hexyn-3-ol, 2-methyl-3-butyn-2-ol. 15 conventional amounts, for example, amounts up to a total of 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyn-3,6-diol. 2,4- about 5 weight % of the composition. 7.9-tetramethyl-5-decyne-4,7-diol and 2,5-dimethyl-3- When exposed to a Substrate comprising a porous dielec hexyne 2,5-diol. tric material, the cleaning compositions of the present inven Exemplary carboxyl group-containing organic com tion do not Substantially change the dielectric constant of the pounds and anhydrides thereof include formic acid, acetic 20 porous dielectric material. In this regard, when exposed to a acid, propionic acid, butyric acid, isobutyric acid, oxalic Substrate comprising a porous dielectric material, the clean acid, malonic acid, Succinic acid, glutaric acid, maleic acid, ing compositions of the present invention preferably does fumaric acid, benzoic acid, phthalic acid, 1,2,3-benzenetri not increase the materials dielectric constant by more than carboxylic acid, glycolic acid, lactic acid, maleic acid, acetic 0.35 and, preferably, not more than 0.25. anhydride and salicylic acid. 25 The cleaning composition of the present invention is Exemplary triazole compounds include benzotriazole, typically prepared by mixing the components together in a o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, carboxyben vessel at room temperature until all solids have dissolved in Zotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole and the aqueous-based medium. dihydroxypropylbenzotriazole. The cleaning composition of the present invention can be In an exemplary embodiment, the corrosion inhibitors 30 used to remove from a substrate undesired residue. It is include one or more of benzotriazole, carboxybenzotriazole, believed that the composition can be used to particularly amino-benzotriazole, D-fructose, catechol, t-butyl catechol, good advantage in cleaning a semiconductor Substrate on L-ascorbic acid, gallic acid, Vanillin, Salicylic acid, diethyl which residue is deposited or formed during the process for hydroxylamine, and poly(ethyleneimine). manufacturing semiconductor devices; examples of Such Preferred copper corrosion inhibitors are selected from 35 residue include resist compositions in the form offilms (both the group consisting of benzotriazole, amino-benzotriazole, positive and negative) and etching deposits formed during L-ascorbic acid, gallic acid, Vanillin, diethylhydroxylamine, dry etching, as well as chemically degraded resist films. The and mixtures thereof. use of the composition is particularly effective when the It is believed that for most applications, the corrosion residue to be removed is a resist film and/or an etching inhibitor will comprise from about 0.1 wt.% to about 15 wt. 40 deposit on a semiconductor Substrate having a metal film % of the composition; preferably it comprises from about exposed Surface. Examples of Substrates that can be cleaned 0.1 wt.% to about 10 wt.%, preferably, from about 0.5 wt. by use of the composition of the present invention without % to about 5 wt.%, and most preferably, from about 0.1 wt. attacking the Substrates themselves include metal Substrates, % to about 1 wt.% or about 0.5 wt.% to about 5 wt.% of for example: aluminum titanium/tungsten; aluminum/sili the composition. 45 con; aluminum/silicon/copper, silicon oxide; silicon nitride; Other Optional Ingredients and gallium/arsenide. Such substrates typically include resi The cleaning composition of the present invention may dues comprising photoresists and/or post etch deposits. also include one or more of the following additives: surfac In addition to being effective when used to remove resist tants, chelating agents, chemical modifiers, dyes, biocides, films and/or etching residues on a semiconductor wafer and other additives. The additive(s) may be added to the 50 having an exposed surface of a metal film, the cleaning extent that they do not adversely affect the pH range of the composition is especially effective when the metal film is composition. made of copper or a copper alloy containing copper as the Another optional ingredient that can be used in the main component and also when a low-dielectric film is used cleaning composition is a metal chelating agent; it can as an interlayer insulating film. An example of a copper alloy function to increase the capacity of the composition to retain 55 containing copper as the main component is one containing metals in Solution and to enhance the dissolution of metallic 90% by weight or more copper, and other elements, for residues. Typical examples of chelating agents useful for this example, Sn, Ag, Mg, Ni, Co, Ti, Si, and Al. Since these purpose are the following organic acids and their isomers metals have low resistances and improve the high-speed and salts: ethylenediaminetetraacetic acid (EDTA), buty operation of elements, but are easily dissolved or corroded lenediaminetetraacetic acid, (1.2-cyclohexylenediamine)tet- 60 by chemicals, the “non-corrosive' properties of the compo raacetic acid (CyDTA), diethylenetriaminepentaacetic acid sition of the present invention are significant. (DETPA), ethylenediaminetetrapropionic acid, (hydroxy The cleaning composition can be used to remove post ethyl)ethylenediaminetriacetic acid (HEDTA), N.N.N',N'- etch and ash, other organic and inorganic residues as well as ethylenediaminetetra(methylenephosphonic) acid polymeric residues from semiconductor Substrates at rela (EDTMP), triethylenetetraminehexaacetic acid (TTHA), 65 tively low temperatures with little corrosive effect. The 1,3-diamino-2-hydroxypropane-N,N.N.N'-tetraacetic acid cleaning composition should be applied to the Surface for a (DHPTA), methyliminodiacetic acid, propylenediaminetet period of time to sufficient to obtain the desired cleaning US 9,536,730 B2 11 12 effect. The time will vary depending on numerous factors, teristic of the cleaning composition that is related to the including, for example, the nature of the residue the tem change in the ratio of the components in the cleaning perature of the cleaning composition and the particular composition. Examples of the variables that may be mea cleaning composition used. In general, the cleaning compo sured and used to determine if it is time to add the replen sition can be used, for example, by contacting the Substrate ishment composition to the cleaning composition include: at a temperature of from about 25°C. to about 85°C. for a the pH or cleaning efficiency or substrate etch rates of the period of time ranging from about 1 minute to about 1 hour composition or the level of the cleaning composition in the followed by rinsing the cleaning composition from the bath. Substrate and drying the Substrate. For the cleaning compositions of this invention that The contacting step can be carried out by any Suitable 10 comprise: a) from about 15% to about 50% by weight of means Such as, for example, immersion, spray, or via a water; b) from about 10% to about 65% by weight or from single wafer process; any method that utilizes a liquid for about 20% to about 65% by weight of a water-miscible removal of photoresist, ash or etch deposits and/or contami organic solvent, wherein the water-miscible organic solvent nants can be used. is not an ether; c) from about 1% to about 50% by weight or The rinsing step is carried out by any suitable means, for 15 from about 1% to about 20% by weight of an amine example, rinsing the Substrate with de-ionized water by compound selected from the group consisting of at least one immersion or spray techniques. In some embodiments, the alkanolamine and at least one aminopropylmorpholine; d) rinsing step is carried out employing a mixture of de-ionized from about 1% to about 25% by weight or from about 1% water and a water-miscible organic solvent such as, for to about 15% by weight of at least one organic acid; and e) example, isopropyl alcohol. from about 0.01% to about 8% by weight or from about The drying step is carried out by any suitable means, for 0.01% to about 7% by weight of a fluoride ion source, the example, isopropyl alcohol (IPA) vapor drying or by cen replenishment composition may comprise: a) from about tripetal force. 20% to about 84% by weight of water; b) from about 15% It will be appreciated by those skilled in the art that the to about 40% by weight of a water-miscible organic solvent, cleaning composition of the present invention may be modi 25 wherein the water-miscible organic solvent is not an ether; fied to achieve optimum cleaning without damaging the and c) from about 1% to about 5% by weight of an amine Substrate so that high throughput cleaning can be maintained compound selected from the group consisting of at least one in the manufacturing process. For example, one skilled in alkanolamine and at least one aminopropylmorpholine. In the art would appreciate that, for example, modifications to Some embodiments, if the cleaning composition further the amounts of some or all of the components may be made 30 comprises from about 1% to about 15% by weight of depending upon the composition of the Substrate being diethylhydroxylamine, the replenishment composition may cleaned, the nature of the residue to be removed, and the further comprised) from about 4% to about 35% by weight particular process parameters used. of diethylhydroxylamine, and said water is present in said In another embodiment of the present invention is pro replenishment composition between from about 20% to vided a replenishment composition for the cleaning compo 35 about 80% by weight. sition of this invention. As the cleaning composition is used The method may further comprise the steps of rinsing the to clean semiconductor Substrates the cleaning composition cleaning composition from the semiconductor Substrate; and is partially removed from the container or bath that holds the drying the semiconductor Substrate, wherein the semicon cleaning composition with each of the Substrates that are ductor Substrate comprises a porous dielectric material hav contacted with the cleaning composition. The cleaning com 40 ing a dielectric constant; and wherein after said contacting, position is typically used to clean a plurality of Substrates rinsing and drying steps the dielectric constant of the porous that are serially and/or simultaneously and/or both serially dielectric material does not increase more than 0.50, or does and simultaneously (in the case of batches of Substrates that not increase more than 0.25. contacted with the cleaning composition followed by one or The preferred components used to form the cleaning a plurality of batches) and then replaced with a fresh 45 compositions are the same preferred components for use in quantity of the cleaning composition. The Substrates are the replenishment composition as described above for the contacted with the cleaning composition by, for example, cleaning composition. The replenishment compositions will spraying the one or more substrates with the cleaning comprise the same components, although typically fewer composition and/or dipping the one or more Substrates into components than the cleaning composition to which it is a bath containing the cleaning composition. The tool used to 50 added and typically the ratios for the components in the clean the Substrates may be for examples, a spray solvent cleaning composition will differ from the ratios of the tool, a wet bench tool or a single wafer tool. Additionally, components in the replenishment composition. The exact typically the method further comprises the step of heating preferred components and the ratios of the components in the cleaning composition ambient temperature to, for the replenishment composition will be a function of the rate example, a temperature between from about 25 or 85°C. or 55 of loss of each particular component either by its removal from about 25 to about 45° C. prior to and/or when con with the substrate (e.g. from the bath) upon completion of tacting the one or more Substrates. The heating of the the contacting step or due to its evaporation from the cleaning composition causes the components of the cleaning composition relative to the other components evaporation. composition to evaporate. The rate of the evaporation of In one embodiment, the replenishment composition is each of the components is typically a function of the boiling 60 added to the cleaning composition by periodic addition to points of each of the components thereby causing the ratio the bath, for example, via a nozzle. A level sensor may be of the components in the cleaning composition to change used to determine how much replenishment composition to over time. It has been determined for the cleaning compo add to the bath. The replenishment composition may be sitions of this invention that it may be beneficial to add a added after each substrate or after each batch of a plurality replenishment composition to cleaning composition after it 65 of substrates are cleaned by contacting them with the has cleaned a set number of Substrates or after a certain cleaning composition. However, after a set number of Sub period of time or upon measurement of a variable charac strates have been treated, by the cleaning composition, the US 9,536,730 B2 13 14 entire bath may require that the cleaning composition be discarded and replaced with fresh cleaning composition, and Comparative the process of contacting and adding can be repeated. The intervals for adding the replenishment composition to the Example A cleaning composition and replacing the entire cleaning com position will vary depending upon the temperature of the Dimethyl acetamide 39.15 cleaning composition, the Substrates to be cleaned, and the DIW 49.75 residues and can be determined by a person of skill in the art. Ammonium Acetate 2.60 Although the present invention has been principally Acetic Acid 2.00 described in connection with cleaning semiconductor Sub 10 strates, the cleaning compositions of the invention can be Ammonium fluoride O.S employed to clean any Substrate that includes organic and Propylene glycol 6.OO inorganic residues.

EXAMPLES 15 92A wt %

The following examples are provided for the purpose of DIW 34.66 further illustrating the present invention but are by no means Glycerol 22.8O intended to limit the same. Propylene glycol 22.90 N,N-diethylhydroxylamine 8.08 General Procedure for Preparing the Cleaning Compositions Lactic acid (88% sol) 7.20 All compositions which are the subject of the present Ammonium fluoride O.S6 Examples were prepared by mixing 500 g of material in a Monoethanol amine 3.80 600 mL beaker with a 1" Teflon-coated stir bar. 25 Compositions of the Substrate Each Substrate used in the present Examples comprised an organosilicate glass (OSG) dielectric material with a tita DIW 27.15 nium nitride capping layer that was deposited on a silicon Propylene glycol (PG) 34.00 nitride substrate. The OSG was etched by reactive ion 30 N,N-diethylhydroxylamine 4.25 etching (RIE) to leave behind OSG lines capped with (DEHA) ethanolamine (MEA) 17.00 titanium nitride. Following RIE, the substrates were treated Acetic Acid 16.00 in a plasma to ash the photoresist. Ammonium fluoride 1.60 Processing Conditions (NH4F) Cleaning tests were run using 305 mL of the cleaning 35 compositions in a 400 mL beaker with a /2" round Teflon stir bar set at 600 rpm. The cleaning compositions were heated to the desired temperature indicated below on a hot plate if necessary. Wafer segments approximately /2"x72" in size 40 DIW 30.86 were immersed in the compositions under the following set PG 45.70 of conditions. N,N-diethylhydroxylamine 8.08 Monoethanol amine 3.80 10 minutes (a 25° C. Paratoluene Sulfonic acid 11.00 20 minutes (a 25°C. Ammonium fluoride O.S6 10 minutes (a 35° C. 45 20 minutes (a 35° C. The segments were then rinsed for 3 minutes in a DI water wt % overflow bath and Subsequently dried using filtered nitrogen. 50 DIW 26.40 They were then analyzed for cleanliness using SEM micros Propylene glycol (PG) 39.00 copy. ethanolamine 17.00 Etch Rate Measurement Procedure (MEA) Acetic Acid 16.00 Coupons of the blanket A1 or blanket Cu wafers were Ammonium fluoride 1.60 measured for metal layer thickness by measuring the resis (NH4F) tivity of the layer by employing a ResMapTM model 273 55 resistivity instrument from Creative Design Engineering, Inc. The coupons were then immersed in the composition at the desired temperature for up to one hour. Periodically the coupons were removed from the composition, rinsed with 60 de-ionized water and dried and the thickness of the metal DIW 31.30 Propylene glycol 45.70 layer was again measured. A graph of the change in thick N,N-diethylhydroxylamine 8.08 ness as a function of immersion time was made and the etch Monoethanol amine 3.80 rate in Angstroms/min was determined from the slope of the Paratoluene sulfonic 11.00 CUV. acid 65 Ammonium fluoride O.12 The following Tables identify the components of the compositions tested and referenced below. US 9,536,730 B2

95W wt % 99V wt % DIW 31.30 Propylene glycol 23.00 5 DIW 34.66 Dimethyl acetamide 22.70 Propylene glycol 45.70 N,N-diethylhydroxylamine 8.08 N,N-diethylhydroxylamine 8.08 Monoethanolamine 3.80 Paratoluene sulfonic 11.OO Monoethanol amine 3.80 acid 10 Lactic acid (88% sol) 7.20 Ammonium fluoride O.12 Ammonium fluoride O.S6

96A wt % 15 99P wt % DIW 34.3 Propylene glycol 49.3 DIW 41.32 (PG) Glycerol 44.75 ethanolamine 8.5 Aminoethoxyethanol 8.3 (MEA) 2O citric acid 4.75 Malonic Acid 6.7 Ammonium fluoride O.88 Ammonium fluoride 1.2 (NH4F)

25 1OOA wt % 96R wt % DIW 34.26 Propylene glycol SO.80 DIW 34.3 (PG) Propylene glycol 46.3 N,N-diethylhydroxylamine 8.08 (PG) (DEHA) ethanolamine 8.5 30 ethanolamine 3.SO (MEA) (MEA) Malonic Acid 6.7 malonic acid 2.80 Ammonium fluoride 1.2 Ammonium fluoride O.S6 (NH4F) (NH4F) glycine 3 35

1 OOB wt % 96W wt % DIW 34.26 DIW 33.8 40 Propylene glycol (PG) S.O.30 Propylene glycol 47.3 N,N- 8.08 Monoethanol amine 8.3 diethylhydroxylamine (DEHA) Malonic Acid 6.7 ethanolamine (MEA) 340 Ammonium fluoride O.9 citric acid 340 glycine 3.0 Ammonium fluoride (NH4F) O.S6 45

97L wt % 1 OOC wt %

DIW 34.66 50 DIW 34.26 Propylene glycol 47.30 Propylene glycol (PG) SO.60 Monoethanol amine 8.30 N,N- 8.08 Malonic Acid 6.70 diethylhydroxylamine (DENA) glycine 3.00 ethanolamine (MEA) 340 Ammonium fluoride O.04 acetic acid 3.10 55 Ammonium fluoride (NH4F) O.S6

99U wt % 1OOD wt % DIW 30.86 60 Propylene glycol 42.70 DIW 34.26 Glycerol 3.00 Propylene glycol (PG) 53.95 N,N-diethylhydroxylamine 8.08 N,N- 8.08 Monoethanolamine 3.80 diethylhydroxylamine (DEHA) Paratoluene sulfonic 11.OO ethanolamine (MEA) 1.75 acid malonic acid 140 Ammonium fluoride O.S6 65 Ammonium fluoride (NH4F) O.S6 US 9,536,730 B2 17 18 -continued 1OOE wt %

DIW 34.26 103B wt % Propylene glycol (PG) 53.70 5 N,N- 8.08 acetic acid 15.05 diethylhydroxylamine (DEHA) ethanolamine (MEA) 1.70 Ammonium fluoride 0.57 citric acid 1.70 Ammonium fluoride (NH4F) O.S6 10

103C wt %

1OOF wt % DIW 34.26 Propylene glycol (PG) 14.10 DIW 34.26 15 N,N-diethylhydroxylamine 8.08 Propylene glycol (PG) 53.85 Diethanolamine 3O.OO N,N- 8.08 Malonic acid 13.00 diethylhydroxylamine (DEHA) Ammonium fluoride O.S6 ethanolamine (MEA) 1.70 acetic acid 1.55 Ammonium fluoride (NH4F) O.S6 2O

106A wt %

DIW 34.26 1OOJ wt % Propylene glycol (PG) 10 N,N-diethylhydroxylamine 8.08 DIW 34.26 25 Diethanolamine (DEA) 30 Propylene glycol (PG) 428O citric acid 17.1 N,N- 8.08 Ammonium fluoride O.S6 diethylhydroxylamine (DEHA) Cyclohexyldiethanol Amine 11...SO malonic acid 2.8O Ammonium fluoride (NH4F) O.S6 30 106B wt %

DIW 34.26 Propylene glycol (PG) 11.35 1OOK wt % N,N-diethylhydroxylamine 8.08 35 Diethanolamine (DEA) 30 DIW 42.26 citric acid 15.75 N,N- 8.08 Ammonium fluoride O.S6 diethylhydroxylamine (DEHA) Cyclohexyldiethanol amine 39.1 malonic acid 10 Ammonium fluoride (NH4F) O.S6 40 112A wt %

DIW 34.26 Propylene glycol (PG) 47.8 1OOL wt % N,N- 8.08 45 diethylhydroxylamine (DEHA) DIW 32.26 Diethanolamine (DEA) 6.5 N,N-diethylhydroxylamine (DEHA) 8.08 Malonic acid 2.8 Cyclohexyldiethanolamine 47.10 Ammonium fluoride O.S6 malonic acid 12.00 Ammonium fluoride (NH4F) O.S6 50

112B wt %

103A wt % DIW 34.26 Propylene glycol (PG) 5240 DIW 34.26 55 N,N-diethylhydroxylamine 8.08 Propylene glycol (PG) 14.10 (DEHA) N,N-diethylhydroxylamine 8.08 Diethanolamine (DEA) 3.2O Diethanolamine 3O.OO acetic acid 1...SO acetic acid 13.00 Ammonium fluoride O.S6 Ammonium fluoride O.S6 60

112C wt % 103B wt % DIW 34.26 DIW 32.43 Propylene glycol (PG) 47.30 Propylene glycol (PG) 9.87 65 N,N-diethylhydroxylamine 8.08 Diethanolamine (DEA) 42.08 (DEHA) US 9,536,730 B2

-continued 112F wt % 112C wt % DIW 33.94 Propylene glycol (PG) 45.9 Diethanolamine (DEA) 6.40 N,N-diethylhydroxylamine 8.08 citric acid 340 (DEHA) Ammonium fluoride O.S6 N-methyldiethanolamine 840 (MDEA) Malonic acid 2.8O Ammonium fluoride O.88 10

101A wt %

DIW 40.71 Propylene glycol (PG) 44.75 113 wt % Aminoethoxyethanol 8.90 citric acid 4.76 15 DIW 32.86 Ammonium fluoride O.88 Propylene glycol (PG) 34.9 Triethanolamine (TEA) 10 Ethanolamine (MEA) 11 Malonic acid 10.68 Ammonium fluoride O.S6 101C wt %

DIW 41.32 Propylene glycol (PG) 428O Diethanolamine (DEA) 1O.OO 114 wt % citric acid (anhydrous) S.OO Ammonium fluoride O.88 25 DIW 29.84 Propylene glycol (PG) 38 Triethanolamine (TEA) 10 Ethanolamine (MEA) 10 citric acid 9.63 115A wt % Malonic acid 1.65 30 mmonium fluoride O.88 DIW 41.32 Propylene glycol (PG) 27.80 Diethanolamine (DEA) 2O.OO citric acid 1O.OO Ammonium fluoride O.88 115 wt % 35 DIW 29.72 Propylene glycol (PG) 36.8 Triethanolamine (TEA) 10 11 SB wt % Ethanolamine (MEA) 11 citric acid 11.6 DIW 41.32 40 Ammonium fluoride O.88 Propylene glycol (PG) 12.8O Diethanolamine (DEA) 3O.OO citric acid 1S.OO Ammonium fluoride O.88 Comparative Example B wt % 45 Water 41.76 Penta methyl 13.88 110A wt % diethyleneamine Triethanolamine 33.62 DIW 33.94 Iminodiacetic acid 3.07 Ammonium Bifluoride 7.67 Propylene glycol (PG) 1O.OO 50 N,N-diethylhydroxylamine 8.08 (DEHA) Diethanolamine (DEA) 32.10 acetic acid 1S.OO Ammonium fluoride O.88 52J wt %

55 DIW 40.52 Glycerol 15 Triethanolamine 32.5 112E wt % (TEA) citric acid 7.98 DIW 33.94 Ammonium fluoride 4 Propylene glycol (PG) 45.30 60 N,N-diethylhydroxylamine 8.08 (DEHA) N-methyldiethanolamine 840 (MDEA) 52O wt % citric acid 340 Ammonium fluoride O.88 65 DIW 37.81 Glycerol 1427 US 9,536,730 B2

-continued 2A wt % 52O wt % 5 DIW 45.78 Triethanolamine (TEA) 37.38 Glycerol 27.16 citric acid 7.14 Triethanolamine (TEA) 8.46 Ammonium fluoride 3.4 Aminoethoxyethanol (AEE) 10.15 citric acid 7.07 10 Ammonium fluoride O.88 Benzotriazole O.S 52L wt %

DIW 41.52 Glycerol 10 15 Triethanolamine (TEA) 32.5 2C wt % citric acid 7.98 Ammonium fluoride 8 DIW 45.78 Glycerol 27.16 S6D wt % 2O Triethanolamine (TEA) 8.46 Aminoethoxyethanol (AEE) 10.15 DIW 45.09 citric acid 7.07 Glycerol 27.3 CMS, s g Triethanolamine (TEA) 10 arboxybenzoriazole Aminoethoxyethanol (AEE) 10 citric acid 6.73 25 Ammonium fluoride O.88 2N wt %

DIW 45.78 Glycerol 27.16 S6S wt % 30 Triethanolamine (TEA) 8.46 Aminoethoxyethanol (AEE) 10.15 DIW 46.01 citric acid 7.07 Glycerol 27.3 Ammonium fluoride O.88 Triethanolamine (TEA) 8.5 Amino-benzotriaole O.S Aminoethoxyethanol (AEE) 10.2 citric acid 7.11 35 Ammonium fluoride O.88

2E wt %

DIW 45.78 56U wt % 40 Glycerol 27.16 Triethanolamine (TEA) 8.46 DIW 46.79 Aminoethoxyethanol (AEE) 10.15 Glycerol 23.4 citric acid 7.07 Triethanolamine (TEA) 8.5 Ammonium fluoride O.88 Aminoethoxyethanol (AEE) 10.2 D-Fructose O.S citric acid 7.11 45 Ammonium fluoride 4

2F wt %

S6O wt % 50 DW 45.78 Glycerol 27.16 DIW 45.87 Triethanolamine (TEA) 8.46 Glycerol 23.4 Aminoethoxyethanol (AEE) 10.15 Triethanolamine (TEA) 10 citric acid 7.07 Aminoethoxyethanol (AEE) 10 Ammonium fluoride O.88 citric acid 6.73 55 Catechol O.S Ammonium fluoride 4

2G wt % 1A wt % 60 DIW 45.78 DIW 4.O.S.S Glycerol 27.16 Glycerol 32.76 Triethanolamine (TEA) 8.46 Triethanolamine (TEA) 8.5 Aminoethoxyethanol (AEE) 10.15 Aminoethoxyethanol (AEE) 10.2 citric acid 7.07 citric acid 7.11 Ammonium fluoride O.88 Ammonium fluoride O.88 65 t-Butyl catechol O.S US 9,536,730 B2 23 24

2H wt % 7A wt % DIW 40.96 DIW 45.78 Glycerol 10 5 Triethanolamine (TEA) 32.5 Glycerol 27.16 citric acid 7.54

Triethanolamine (TEA) 8.46 AmmoniumL-AScorbic acidfluoride 81 Aminoethoxyethanol (AEE) 10.15 citric acid 7.07 10 Ammonium fluoride O.88 L-AScorbic acid O.S 7B wt %

DIW 39.68 15 Glycerol 10 Triethanolamine (TEA) 32.5 2I wt % citric acid 6.82 Ammonium fluoride 8 DIW 45.78 L-AScorbic acid 1 Glycerol 27.16 Triethanolamine (TEA) 8.46 2O Aminoethoxyethanol (AEE) 10.15 citric acid 7.07 Ammonium fluoride O.88 Gallic acid O.S 7C wt %

25 DIW 40.96 Glycerol 10 Triethanolamine (TEA) 32.5 2 wt % citric acid 7.54 Ammonium fluoride 8 DIW 45.78 gallic acid 1 Glycerol 27.16 Triethanolamine (TEA) 8.46 30 Aminoethoxyethanol (AEE) 10.15 citric acid 7.07 Ammonium fluoride O.88 Vanillin O.S 7D wt % 35 DIW 39.68 Glycerol 10 Triethanolamine (TEA) 32.5 2K wt % citric acid 6.82 Ammonium fluoride 8 DIW 45.78 Gallic acid 3 Glycerol 27.16 40 Triethanolamine (TEA) 8.46 Aminoethoxyethanolcitric acid (AEE) 10.157.07 The following tables summarize the copper etch rate Ammonium fluoride O.88 (E/R) data: Salicylic acid O.S 45 Product Formulation 5% pH Cu ER (A/min) 52J 7.81 2.4 2L. wt % 52O 8.00 2.3 S2L 7.81 2.8 DIW 45.78 50 S6D 8.38 4.0 Glycerol 27.16 S6S 8.23 1.8 Triethanolamine (TEA) 8.46 56U 8.14 2.3 Aminoethoxyethanol (AEE) 10.15 S6O 8.46 2.3 citric acid 7.07 E0O2O1-1A 8.21 1.2 Ammonium fluoride O.88 Diethylhydroxylamine O.S 55

Product Formulation 5% pH Cu ER (A/min) 2M wt % 2A 8.22 O.3 DIW 45.78 60 C. 8.16 5.5 Glycerol 27.16 2N 8.33 1.7 Triethanolamine (TEA) 8.46 2E 8.26 4.6 Aminoethoxyethanol (AEE) 10.15 2F 8.23 6.3 citric acid 7.07 2G 8.23 4.6 Ammonium fluoride O.88 2H 8.15 3 Poly(ethyleneimine) (P3143) O.S 65 2I 8.16 4.2 2J 8.14 3.7 US 9,536,730 B2

-continued Results of Film Loss Product Formulation 5% pH Cu ER (A/min) 1OOA 1 OOB 1OOC 1 OOD 1OOE 10OF 2K 8.22 6.6 2L. 8.3 3.2 Cu 23.6 79.4 77.4 28.9 113.4 88.2 2M 8.4 5.9 SiN 2.7 2.06 O.9S 1 7.02 4.87 7A 7.79 1.8 TEOS O.3 1 O.3 O.3 1.3 1 7B 7.76 1.5 7C 7.78 1.6 Note: 7D 7.77 2.0 1. Film loss in A was measured after 15 mins in each cleaning composition at 35° C. 10 As is evident, a number of the formulations tested exhibit an excellent copper etch rate. A lower Cu E/R value evi TEOS (undoped and dences a better copper etch rate. In particular, compositions pH in 5% Cu loss (a) undensified) loss (a) Formulations Solution 35 C./15 min, A 35 C./15 min, A providing a copper etch rate of 4 A/min or less, 3 A/min or 15 less, or 2 A/min or less are preferred. 112A 8.16 24 15 112B 8.36 118 <1 112C 8.22 89 <1 Comparative Examples 112E 8.31 76 10 101A 8.2O 16S 14 101C 8.30 191 <1 Use of Ether Solvent Showing Increase in Cu Etch 115A 8.21 126 21 Rate 11 SB 8.13 72 16 1O3C 8.22 17 17 As comparative examples, two of the examples provided 106B 8.27 61 9 above, 52J and 56S, were evaluated by replacing a portion 110A 8.37 15 14 or all of the glycerol with an ether, dipropylene glycol 25 pH Stability monomethyl ether (DPM). The compositions remained oth pH measured is a 5% aqueous solution of the formulations erwise identical.

Day 1 Day 2 Day 3 Day 4 Day 5 Day 8 Product Formulation Cu ER (A/min) 30 1OOA 8.22 8.19 8.25 8.22 8.23 8.29 52J As above 2.4 1OOB 8.24 8.32 8.35 8.31 8.3 8.31 Comp-69A 52J replacing all glycerol with 5.8 1OOC 8.21 8.28 8.26 8.24 8.24 8.31 DPM (15 wt %) 1OOD 8.28 8.32 8.34 8.33 8.34 8.32 Comp-69B 52J replacing half of glycerol 4.4 1OOE 8.16 8.25 8.22 8.27 8.28 8.26 with DPM (7.5 wt %) 35 1OOF 8.44 8.48 841 8.45 8.45 8.45 S6S As above 1.8 Comp-69C 56S replacing all glycerol 47.7 with DPM (15 wt %) Comp-69D 56S replacing half of glycerol 26.3 Compare with conventional low pH fluoride stripper with DPM (7.5 wt %) Comparative Example A. Example 95O showed much lower 40 film loss on dielectric blankets. Dielectric Film Loss Test These results demonstrate that the Cu E/R significantly increased when a portion or all of the glycerol was replaced Comp. Ex. A (a) 25 C.) 53.5 57.1 39 59 with DPM (an ether solvent). Thus, these results suggest that Example 95O (a) 35 C.) 3.7 2.7 4.4 7.6 an ether solvent can produce an adverse impact on the 45 copper etch rate when employed in the compositions dis unit: A, 15 mins time frame closed herein. The dielectric constant of each sample film was deter Procedure: Film Loss Measurements mined according to ASTM Standard D150-98. The capaci 1. Measure the thickness before chemical immersion. tance-voltage of each film were obtained at 1 MHz with a 2. Immersion test was carried out in beaker with magnetic 50 Solartron Model SI 1260 Frequency Analyzer and MSI stir agitation (500 rpm) at 35 C for 15 mins. Electronics Model Hg 401 single contact mercury probe. 3. Chemical immersion was followed by 3 minutes DI The error in capacitance measurements and mercury elec rinse and N2 blow dry. trode area (A) was less than 1%. The substrate (wafer) 4. Measure the thickness after chemical immersion. capacitance (Cs), background capacitance (C) and total 55 capacitance (C) were measured between +20 and -20 volts 5. Film loss=Step 4-Step 1 and the thin film sample capacitance (CO was calculated by An ellipsometer for SiN and TEOS thickness measure Equation (1): ments and a 4 point probe for Cu was employed to make the measurements as Summarized in the Table below. C=Cs (C-C) Cs-(C-C) Equation (1) The dielectric constant of each film was calculated by 60 Equation (2) wherein d is the film thickness, A is the mercury Ellipsometer 4 Point Probe electrode area, and 6 is the dielectric constant in vacuum: Company SCI (Scientific Computing CDE (Creative Design Csd Equation (2) International) Engineering) Model FilmTek 2000SE ResMap 273 65 The total error of the dielectric constant of the film was expected to be less than 6%. US 9,536,730 B2 27 28 Kshift of 95O was lower than Comparable Example B on of benzotriazole, amino-benzotriazole, L-ascorbic acid, 40/45 nm dielectric film. The results are in the following gallic acid, Vanillin, diethylhydroxylamine, and mix table. tures thereof. K Shift of Comparable Example B and Example 95O 2. The composition of claim 1 wherein the water-miscible organic solvent is selected from the group consisting of propylene glycol, glycerol, dimethylacetamide, tetrahydro 27O Sec 27O Sec 15 mins 15 mins furyl alcohol, ethylene glycol, hexylene glycol, and mixtures Comp. Example B (40 C.) thereof. 3. The composition of claim 2 wherein the water-miscible Before 2.73 2.71 2.71 2.74 10 organic solvent is dimethylacetamide. After 3.05 3.07 3.12 3.15 4. The composition of claim 2 wherein the water-miscible Delta K O.32 O.36 O41 O41 organic solvent is propylene glycol. Example 95O (35 C.) 5. The composition of claim 2 wherein the water-miscible Before 2.72 2.73 2.71 2.72 organic solvent is glycerol. After 2.88. 2.9 2.93 2.91 15 6. The composition of claim 1 wherein the fluoride ion Delta K O16 O.17 O.22 O.19 Source is selected from the group consisting of ammonium fluoride and a quaternary ammonium compound. Example 95O, shown in FIG. 1, can be also applied to 7. The composition of claim 6 wherein the fluoride ion Aluminum Back End of the Line (Al BEOL) clean. FIG. 1 Source is ammonium fluoride. demonstrates that the residue on an Al pattern wafer can be 8. The composition of claim 6 wherein the fluoride ion effectively removed at 25° C. for 1 min. Source is a quaternary ammonium compound selected from Examples of replenishment formulations include the fol the group consisting of tetramethylammonium fluoride and lowing compositions 43A and 93B tetrabutylammonium fluoride. 9. The composition of claim 1 wherein the amine com 25 pound is an alkanolamine selected from the group consisting 43A wt % of N-methylethanolamine (NMEA), monoethanolamine DIW 55.45 (MEA), diethanolamine, mono-, di- and triisopropa Propylene glycol (PG) 29.83 nolamine, 2-(2-aminoethylamino)ethanol. 2-(2-aminoeth N,N-diethylhydroxylamine 12.27 oxy)ethanol, triethanolamine, N-ethyl ethanolamine, N.N- (DEHA) 30 dimethylethanolamine, N,N-diethyl ethanolamine, ethanolamine (MEA) 2.45 N-methyl diethanolamine, N-ethyl diethanolamine, cyclo hexylaminediethanol, and mixtures thereof. 10. The composition of claim 9 wherein the alkanolamine is monoethanolamine. 93B wt % 35 11. The composition of claim 9 wherein the amine com DIW 33.15 pound is aminopropylmorpholine. ethanolamine (MEA) 4.5 12. The composition of claim 9 wherein the amine com N,N-diethylhydroxylamine 35 pound is triethanolamine. (DEHA) Propylene glycol (PG) 27.35 13. The composition of claim 9 wherein the amine com 40 pound is a mixture of triethanolamine and 2-(2-aminoeth oxy)ethanol. The foregoing examples and description of the preferred 14. The composition of claim 1 wherein the composition embodiments should be taken as illustrating, rather than as consists of limiting the present invention as defined by the claims. As a) from about 35% to about 50% by weight of water; will be readily appreciated, numerous variations and com 45 b) from about 10% to about 30% by weight of the binations of the features set forth above can be utilized water-miscible organic solvent; without departing from the present invention as set forth in c) from about 8% to about 50% by weight of the amine the claims. Such variations are not regarded as a departure compound selected from the group consisting of a at from the spirit and scope of the invention, and all Such least one alkanolamine and aminopropylmorpholine; variations are intended to be included within the scope of the 50 d) from about 6% to about 10% by weight of the organic following claims. acid; What is claimed is: e) from about 1% to about 8% by weight of the fluoride 1. A composition useful for removing residue from a ion source; and semiconductor Substrate, the composition consisting of: f) optionally, from about 0.1% to about 15% by weight of a) from about 15% to about 50% by weight of water; 55 a corrosion inhibitor selected from the group consisting b) from about 10% to about 65% by weight of a water of benzotriazole, amino-benzotriazole, L-ascorbic acid, miscible organic solvent; gallic acid, Vanillin, diethylhydroxylamine, and mix c) from about 1% to about 50% by weight of an amine tures thereof. compound selected from the group consisting of a at 15. A method for removing residue from a semiconductor least one alkanolamine and aminopropylmorpholine; 60 Substrate, the method comprising the steps of: d) from about 1% to about 25% by weight of an organic contacting the semiconductor Substrate with a cleaning acid; composition of claim 1, wherein the semiconductor e) from about 0.01% to about 8% by weight of a fluoride Substrate comprises a porous dielectric material having ion Source, wherein the water-miscible organic solvent a dielectric constant; is not an ether, and 65 rinsing the cleaning composition from the semiconduc f) optionally, from about 0.1% to about 15% b weight of tor Substrate; and a corrosion inhibitor selected from the group consisting drying the semiconductor Substrate, US 9,536,730 B2 29 30 wherein the dielectric constant of the porous dielectric solvent is not an ether; c) from about 1% to about 20% by material does not increase more than 0.50. weight of an amine compound selected from the group 16. The method of claim 15 wherein the dielectric con consisting of at least one alkanolamine and at least one stant of the porous dielectric material does not increase more aminopropylmorpholine; d) from about 1% to about 25% by than 0.25. weight of at least one organic acid; e) from about 0.01% to 17. The method claim 15 wherein the cleaning composi about 8% by weight of a fluoride ion source; and f) from tion provides a copper etch rate of 4 A/min or less. about 1 to about 15% by weight of diethyl hydroxylamine, 18. A replenishment composition to be added to a cleaning wherein said contacting step results in a loss of a portion of composition, said replenishment composition consisting of said cleaning composition; and adding a replenishment a) from about 20% to about 84% by weight of water; b) from 10 composition to said cleaning composition; said replenish about 15% to about 40% by weight of a water-miscible organic solvent, wherein the water-miscible solvent is not an ment composition consisting of a composition of claim 18. ether; c) from about 1% to about 5% by weight of an amine 20. The method of claim 19 further comprising the steps compound selected from the group consisting of at least one of rinsing the cleaning composition from the semiconductor alkanolamine; at least one aminopropylmorpholine; and 15 Substrate; and drying the semiconductor Substrate, wherein optionally, from about 4% to about 35% by weight of diethyl the semiconductor Substrate comprises a porous dielectric hydroxylamine, and said water is from about 20 to about material having a dielectric constant; and wherein after said 80% of the replenishment composition. contacting, rinsing and drying steps the dielectric constant of 19. A method for removing unwanted residues from a the porous dielectric material does not increase more than semiconductor Substrate comprising the steps of contacting O.50. the semiconductor Substrate with a cleaning composition 21. The method of claim 20 wherein the dielectric con consisting of: a) from about 15% to about 50% by weight of stant of porous dielectric material does not increase more water; b) from about 10% to about 65% by weight of a than 0.25. water-miscible organic solvent, wherein the water-miscible