Compositions comprising primary and secondary surfactants for use in cleaning or washing products

Abstract

The present invention describes a composition for cleaning or washing a product, preferably a product used in the semiconductor industry, comprising an ionic compound containing one or more fluoroalkyl groups as a primary surfactant, and at least one nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups as a secondary surfactant, and the corresponding use of the composition. The present invention further describes a method for producing a cleaned or washed product, preferably a product used in the semiconductor industry, the product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or less than 50 nm, the method comprising the step of cleaning or washing the product with the composition of the present invention.

Description

[0001] The present invention relates to a composition comprising an ionic compound containing one or more fluoroalkyl groups as a primary surfactant and at least one nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups as a secondary surfactant, the composition being used for cleaning or washing products, preferred products, and the corresponding uses of the composition. The present invention also relates to a method for producing a cleaned or washed product, preferably a product used in the semiconductor industry, the product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or less than 50 nm, the method comprising the step of cleaning or washing the product with the composition of the present invention.

[0002] In the process of producing integrated circuits (ICs) with large-scale integration (LSI), very large-scale integration (VLSI) and ultra-large-scale integration (ULSI), patterned material layers are produced by photolithography techniques, such as patterned photoresist layers; patterned insulating material layers containing or consisting of titanium nitride, tantalum or tantalum nitride; patterned multi-stacked material layers containing or consisting of a stack of, for example, alternating polysilicon and silicon dioxide layers; and patterned dielectric material layers containing or consisting of silicon dioxide or low-k or ultra-low-k dielectric materials. Today, these patterned material layers contain structures with dimensions even below 22 nm and high aspect ratios. These specifications also apply to the present invention as defined herein.

[0003] The aspect ratio "H:W" contained in the patterned material layer referred to herein is defined by the ratio between the height (H) of the features of the patterned material layer and the width (line width, W) of the features of the patterned material layer (consistent with the conventional meaning in the art). Therefore, a structure with a high aspect ratio is a structure whose height extension value is greater than its width extension value.

[0004] Photolithography is a method in which a pattern cut into a mask is projected onto a substrate, particularly a semiconductor substrate (e.g., a semiconductor wafer). Semiconductor photolithography typically comprises the steps of coating a layer of photoresist on the top surface of the semiconductor substrate and exposing the photoresist to actinic radiation, particularly UV radiation of a wavelength of, for example, 193 nm, via a mask. These principles also apply to the present invention described herein. In order to extend 193 nm photolithography to 22 nm and 15 nm technology nodes, immersion photolithography has been developed as a resolution improvement technology. In this technology, the air gap between the final lens of the optical system and the photoresist surface is replaced with a liquid medium having a refractive index greater than 1, such as ultrapure water having a refractive index of 1.44 for a wavelength of 193 nm. This technology can also be applied to the method according to the present invention or used in conjunction with the present composition described herein. However, in order to avoid leaching, water absorption, and pattern degradation, an insulating coating or a water-resistant photoresist must be used.

[0005] In addition to 193 nm immersion lithography, other irradiation techniques with significantly shorter wavelengths are being considered to meet the need to further scale down the feature sizes to be printed at the 20 nm node and below; electron beam (e-beam) exposure and extreme ultraviolet lithography (EUV) with a wavelength of about 13.5 nm appear to be promising candidates to replace immersion lithography in the future. After exposure to actinic radiation, the subsequent process flow is independent of the photolithography method used (e.g., UV photolithography, immersion photolithography, or EUV photolithography as described above), and can therefore be used in the method or process according to the present invention.

[0006] Typically and as known to those skilled in the art, structures with high aspect ratios and structures with line widths equal to or below 50 nm are produced by directing an intense light beam through a photomask onto a photoresist (i.e., a chemically deposited layer on a substrate). The basic sequence of the photolithography process is typically and for example divided into several process steps, for example in many cases and situations into the following process steps:

[0007] 1) cleaning the wafer; 2) preparation; 3) coating of photoresist; 4) exposure and post-exposure baking; 5) development and cleaning; 6) hard baking; and 7) subsequent processes such as plasma etching.

[0008] Subsequent process steps for producing the device are then usually performed. As is apparent to those skilled in the art, some of the process steps described above may be omitted, modified, or other process steps may be inserted in addition to the process steps listed above to adapt the photolithography process to actual production needs.

[0009] The method and use according to the invention are preferably part of a process for producing a cleaned or rinsed product comprising a substrate and a patterned material layer supported thereon, the process comprising one or all of the process steps as described above. With respect to the basic process of the photolithography process described above, the invention (use, method and composition) preferably relates to process step 5.

[0010] In process step 1 (cleaning the wafer), different chemical treatments are applied to the wafer surface to remove substances (contamination) absorbed on the wafer surface.

[0011] In process step 2 (preparation), the wafer is heated to at least 150°C to remove moisture absorbed on the surface, optionally followed by treatment with hexamethyldisilazane (HMDS) to passivate ("hydrophobize") the surface (capping residual OH groups with methyl groups). The passivated surface is used to prevent diffusion of water between the wafer surface and the photoresist layer in the later stages of the photolithography process.

[0012] In process step 3 (coating photoresist), a photoresist layer is deposited onto the wafer by spin coating. A detailed description and discussion of this process step can be found in US 4267212A. The thickness of this layer can vary from about 10 nm for EUV photoresists to about 100 nm for deep ultraviolet (DUV) photoresists, and can reach up to several microns for early photoresists and micromachining applications. After evaporation of the solvent, the deposited photoresist layer is optionally pre-baked at a temperature of typically about 100°C.

[0013] In process step 4, an intense beam of light is directed through a photomask so that only specific points of the photoresist layer are exposed to light. Depending on the nature of the photoresist (positive or negative), the exposed or unexposed areas of the photoresist are removed in the next process step (development). A post-exposure bake is often performed to aid in the chemical expansion of the photoresist.

[0014] In process step 5 (development and cleaning) and in accordance with the present invention, a developer solution is contacted with the photoresist to remove the exposed (positive photoresist) or unexposed (negative photoresist) areas of the photoresist layer. Thus, a patterned photoresist layer (positive or negative) corresponding to the pattern of the photomask remains on the wafer (substrate). A typical developer solution contains tetramethylammonium hydroxide (TMAH) for positive photoresists and an organic solvent for negative photoresists.

[0015] After the developer solution has been on the photoresist for a suitable time, a cleaning composition is applied (wet-on-wet) to prevent, remove or reduce specific defects (e.g. watermark defects, residual residues from the developer solution, pattern collapse). Optionally, it is also possible to have an additional water rinse step between the developer solution and the cleaning formulation. The application of the cleaning composition is particularly relevant for products with line-space structures with small line widths and high aspect ratios. Subsequently, the substrate is usually spin-dried and then transferred to the next process step.

[0016] In process step 6 (hard bake), the wafer supporting the patterned photoresist layer may optionally be "hard baked," typically at a temperature of 120° C. to 180° C. After the hard bake, the residual photoresist layer has solidified and is therefore more resistant to chemical treatment and / or physical stress.

[0017] Subsequent process steps 7 (e.g., plasma etching) transfer the target structure of the photoresist into the wafer substrate. The etching step typically removes the dielectric layer and / or hard mask layer (silicon oxide or low-k layer (e.g., silicon oxide, titanium nitride, low-k layer (carbon-doped silicon oxide)) between the photoresist layer and the wafer.

[0018] Independent of the exposure technique, wet chemical processing of the small patterns described above involves several issues: As technology advances and dimensional requirements become increasingly stringent, photoresist patterns are required to include relatively thin and tall photoresist structures or features on the substrate, i.e., features with high aspect ratios. These structures may be subject to bending and / or collapse, especially during cleaning or rinsing processes, due to, for example, excess capillary forces of residual liquid or solution from the cleaning or rinsing solution between adjacent photoresist features, especially during spin drying processes. The maximum stress σ between small features caused by capillary forces can be described according to Namatsu et al., Appl. Phys. Lett. 66 (20), 1995 as follows:

[0019]

[0020] Where γ is the equilibrium surface tension of the fluid, θ is the contact angle of the fluid on the substrate on which the patterned material layer is supported, i.e., the contact angle between the fluid and the structure, such as the photoresist (also referred to in the literature as the "liquid internal contact angle"), D is the distance between the features of the patterned material layer (also referred to as the "gap"), W is the width (line width) of the features of the patterned material layer, and H is the height of the features of the patterned material layer (parameters H and W determine the aspect ratio).

[0021] One approach to reducing the maximum stress σ of the cleaning and rinsing steps may include using a photoresist with a modified polymer to be more hydrophobic. However, this approach may reduce the wettability of the photoresist pattern by the cleaning and rinsing solutions, which is not preferred.

[0022] In another method of reducing the maximum stress σ, the surface tension γ of the fluid (both dynamic and equilibrium) must be reduced. To reduce the surface tension of a fluid or liquid, a surfactant is typically added to the fluid or liquid.

[0023] Another way to reduce the maximum stress σ is to reduce the value of cos θ by adjusting the value of the contact angle θ accordingly.

[0024] Another problem with conventional photolithography processes is line edge roughness (LER) and line width roughness (LWR) due to photoresist and optical resolution limitations. LER includes horizontal and vertical deviations from the ideal form of a feature. In particular, as critical dimensions shrink, LER becomes more problematic and has negative effects, such as increased transistor leakage current, thereby reducing the performance of integrated circuit (IC) devices.

[0025] As dimensions shrink, particle removal becomes a critical factor in order to reduce defects. The latter also applies to photoresist patterns and other patterned material layers produced during the production of optical devices, micromechanical and mechanical precision devices.

[0026] An additional problem with conventional photolithography processes is the presence of watermark defects. Watermarks may form on the photoresist because deionized water or defect cleaning solutions cannot spin away from the hydrophobic surface of the photoresist. Watermarks have a detrimental effect on yield and IC device performance.

[0027] Another problem is the occurrence of so-called "spot defects". These defects are caused during UV exposure and / or photoresist development and usually have the form of massed "pit-like" openings on one or more top layers (e.g. polymer layers and photosensitive layers) on the photoresist. Small particles or other insoluble materials can be trapped in these openings and lead to inefficient particle removal or opening blockage. In particular, hydrophobic fragments or hydrophobic molecular aggregates are absorbed in or on the sides of the defects. These residual particles, fragments or aggregates cause problems in subsequent process stages.

[0028] Another problem with conventional photolithography processes is the absorption of solvents by the photoresist layer or the patterned material layer, which causes these layers to swell. As a result, very close patterns, especially patterns with line-space structures with a line width equal to or below 50 nm, are in direct contact with each other after swelling. Moreover, even after developing, cleaning or washing the product, especially the product of the present invention, the swollen patterns that are in direct contact with each other will subsequently adhere together. Therefore, the swelling of the photoresist limits the minimum line-space size that can be achieved for the product, especially the product defined in the present invention.

[0029] Here and in the context of the present invention, the term "patterned material layer" refers to a layer supported on a substrate. The supported layer has a specific pattern, which preferably has a line-space structure with a line width equal to and lower than 50nm, wherein the supporting substrate is usually a semiconductor substrate, such as a semiconductor wafer. The term "patterned material layer having a line-space structure with a line width equal to or lower than 50nm" means that this patterned material contains a line-space structure with a line width of 50nm and a line-space structure with a line width less than 50nm (narrower), in particular a line-space structure with a line width equal to or lower than 32nm or a line-space structure with a line width equal to or lower than 22nm. In a product comprising a substrate and a patterned material layer having a line-space structure with a line width of 50nm and lower than 50nm supported thereon (i.e., in a product subjected to the production method, use and / or treatment of the present invention), the ratio between the line width and the gap width between two adjacent lines is preferably less than 1:1, more preferably less than 1:2. Those skilled in the art know that patterning material layers with such low "line width / space width" ratios requires extremely delicate handling during production.

[0030] The line width of the line-gap structure of the patterned material layer can be easily detected by scanning electron microscopy, for example by scanning electron microscopy using a Hitachi CG 4000 scanning electron microscope.

[0031] Typically, the patterned material layer processed according to the present invention is formed by depositing a polymer photoresist onto a support and then exposing the supported photoresist layer to actinic radiation via a mask. After developing the exposed photoresist layer with a developer solution, a patterned material layer is produced. In some cases, a post-exposure bake (PEB) is performed before developing with a developer solution. A typical developer solution is, for example, an aqueous solution comprising TMAH (see, for example, WO 2014 / 091363, p.23, 1.10).

[0032] Several exemplary publications of the prior art describe ionic or nonionic surfactants and / or compositions for use in cleaning or washing products:

[0033] Document WO 2010 / 149262 A1 (equivalent to US 2012 / 111233 A1) relates to fluorosurfactants.

[0034] Document WO 2012 / 084118 A1 relates to derivatives of perfluoroalkoxy sulfosuccinate as surface-active surfactants.

[0035] Document WO 2012 / 101545 A1 relates to the use of surfactants having at least three short-chain perfluorinated groups for producing integrated circuits having patterns with line-gap dimensions below 50 nm.

[0036] Document WO 2013 / 022673 A2 relates to perfluoroalkylsulfonamide surfactants for photoresist cleaning solutions.

[0037] Document WO 2015 / 004596 A1 relates to the use of surfactants having at least three short-chain perfluorinated groups in formulations for photomask cleaning.

[0038] Document WO 2017 / 009068 A1 relates to defect-reducing cleaning solutions containing ammonium salts of sulfoesters.

[0039] Document GB 1 573 208 describes surface treatment agents suitable for intermediate products of semiconductor devices.

[0040] Document JPS5064208A relates to the production of fluorine compounds.

[0041] Both documents JPS50101306A and JPS50101307A deal with fluorinated compounds.

[0042] Document JPS5952520A relates to a fluorinated surfactant which is prepared by reacting a polyhydroxy compound with a perfluoroolefin trimer compound.

[0043] In view of the prior art, there remains a need for compositions suitable for improved cleaning or rinsing of products used in the semiconductor industry that include substrates, such as products that support patterned material layers on the substrates, the patterned material layers having line-space structures with line widths equal to or less than 50 nm, and corresponding methods of producing such products.

[0044] Therefore, the main object of the present invention is to provide a composition that can be used to improve the cleaning or washing of products containing substrates used in the semiconductor industry, such as products on which a patterned material layer is supported, the patterned material layer having a line-space structure with a line width equal to or lower than 50nm. The use of the composition should allow the prevention of pattern collapse, the reduction of line edge roughness, the prevention or reduction of watermark defects, the prevention or reduction of photoresist swelling, the prevention or reduction of spot defects and / or the removal of particles, and should ideally achieve improvements in one or more, preferably all, of the aforementioned cleaning or washing results when compared to known compositions of the prior art.

[0045] Another object of the present invention is to provide a corresponding method for producing a cleaned or rinsed product, the product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or lower than 50 nm.

[0046] It was found that the primary and other objects of the present invention are achieved by a composition for cleaning or washing products, preferably products used in the semiconductor industry, comprising:

[0047] (A) an ionic compound of formula (I) as a primary surfactant,

[0048]

[0049] in

[0050] X is a cation, preferably a metal-free monovalent cation, more preferably selected from the group consisting of:

[0051] Proton,

[0052] and

[0053] Group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched (ie, linear) C 1-6 Alkyl (i.e., an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms);

[0054] One of Y1 and Y2 is an anionic polar group, and the other is hydrogen,

[0055] The radicals Z1, Z2 and Z3 are each independently of one another:

[0056] - branched or unbranched C 1-10 Alkyl (i.e., an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms),

[0057] or (preferred)

[0058] - With R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e A group of structures, wherein:

[0059] R 1 , R 2 , R 3 and R 4 are independently hydrogen or branched or unbranched C 1-4 Alkyl (i.e. an alkyl group having 1, 2, 3 or 4 carbon atoms),

[0060] R i Is branched or unbranched C 1-10Alkyl (i.e., an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms),

[0061] A is oxygen, sulfur and / or (preferably or) -N(H)-, more preferably oxygen (if more than one A is present, the meaning of each A is independent of the meaning of any other A),

[0062] c is an integer in the range of 0 to 10,

[0063] d is an integer in the range of 0 to 10,

[0064] e is an integer ranging from 1 to 5,

[0065] The premise is that c and d are not 0 at the same time (that is, c+d>0),

[0066] and wherein at least one of the groups Z1, Z2 or Z3 is a group having the structure R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e -group;

[0067] and

[0068] (B) at least one nonionic compound containing one or more polyalkoxy groups and / or polyalkyleneoxy groups as a secondary surfactant.

[0069] The invention as well as preferred embodiments and preferred combinations of parameters, features and elements thereof are defined in the appended claims. Preferred aspects, details, modifications and advantages of the invention are also defined and explained in the following description and in the examples described hereinafter.

[0070] The composition of the present invention is found to be able to show excellent cleaning and / or washing results on a substrate on which a patterned material layer having a line-space structure with a line width equal to or less than 50 nm is supported, and at the same time can excellently prevent pattern collapse, reduce line edge roughness, prevent or reduce watermark defects, prevent or reduce photoresist swelling, prevent or reduce spot defects and / or excellently remove particles. In particular, it is found that cleaning or washing with the composition of the present invention can significantly reduce pattern collapse and ideally prevent pattern collapse.

[0071] Herein, preventing pattern collapse, reducing line edge roughness, preventing or reducing watermark defects, preventing or reducing photoresist swelling, preventing or reducing spot defects and / or excellent particle removal are also collectively referred to as "reducing defects".

[0072] Therefore, the composition according to the present invention is particularly suitable as a defect-reducing cleaning solution for semiconductor substrates.

[0073] It is thus contemplated that the combination of a primary ionic surfactant (A) containing one or more fluoroalkyl groups and at least one secondary nonionic surfactant (B) containing one or more polyalkoxy and / or polyalkyleneoxy groups according to the present invention provides a synergistic effect of improving cleaning and defect reduction cleaning results for products used in the semiconductor industry, the products comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or less than 50 nm. Without wishing to be bound by theory, it is currently contemplated that the primary ionic surfactant (A) provides reduced surface tension, fast dynamic surface tension, good wettability (especially good wettability of the patterned material layer having a line-space structure with a line width equal to or less than 50 nm) and excellent defect reduction to this composition. On the other hand, it is currently envisioned that the secondary non-ionic surfactant (B) beneficially adjusts the degree of interaction between the primary ionic surfactant (A) and a patterned material layer (especially a photoresist) having a line-space structure with a line width equal to or less than 50 nm, thereby improving the solubility and / or colloidal stability of the primary ionic surfactant (A) in the carrier solvent (usually water), minimizing the adhesion of particles on the surface of the patterned material layer and / or reducing the redeposition of such particles on the surface.

[0074] In addition, it is currently contemplated that the compositions of the present invention reduce two factors that affect the maximum stress σ, which is caused by capillary forces between small features (i.e., features with high aspect ratios) such as photoresists on semiconductor substrates (see above), namely the fluid equilibrium surface tension γ, and the cosθ of the contact angle θ of the fluid on the substrate on which the patterned material layer is supported (i.e., the contact angle of the fluid with the structure such as photoresist, see above), and this reduction makes the compositions of the present invention particularly effective in reducing or avoiding pattern collapse phenomena.

[0075] It has been further found that the secondary surfactant having a nonionic structure used in the composition of the present invention has the following advantages: only few (if any) unwanted particles are formed in the composition, and the formation of crystals in the composition is reduced or avoided. The particles or crystals formed in the composition will have the following effect: adversely affecting the cleaning or washing effect of a substrate having a patterned material layer having a line-space structure with a line width equal to or less than 50 nm supported thereon, because the particles and / or crystals from the composition may be deposited on the line-space structure.

[0076] It has further been found that nonionic secondary surfactants containing one or more polyalkoxy and / or polyalkyleneoxy groups are particularly well suited for interacting with patterned material layers (especially photoresists) having line-space structures with line widths equal to or below 50 nm for the purpose of cleaning, washing or defect reduction. It has also been found that the structure and length of the polyalkoxy and / or polyalkyleneoxy groups as defined herein (preferably a length in the range of 1 to 100, more preferably 1 to 50, even more preferably 5 to 30 alkyleneoxy repeating units) have a beneficial effect on the use of the composition of the present invention.

[0077] Another advantage of the present invention is that the primary surfactant of formula (I) in the composition of the present invention shows improved environmental safety, since it is not envisaged to degrade into long-chain perfluoroalkyl carboxylic acids and / or perfluoroalkyl sulfonic acids with bioaccumulation potential, thereby allowing the production of compositions for cleaning or washing products with at least a reduced content of perfluoroalkyl surfactants that are potentially harmful to the environment.

[0078] According to the present invention, in the compound of formula (I), each R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e -group is preferably connected via the right end indicated by the bond line next to the subscript "e" (if applicable, via the group or the last group [-C(R 1 )(R 2 )-] or [-C(R 3 )(R 4 )-] is bonded to the oxygen atom of the carboxyl group in the compound of formula (I).

[0079] According to the present invention, in the compounds of formula (I), preferably the groups Z1, Z2 and Z3 are each independently of one another a group having the structure R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e -. In the groups Z1, Z2 and Z3, each independently of the other is a group having the structure R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e -, the groups Z1, Z2 and Z3 may be identical, or they may be different from each other. In a preferred variant of the present invention, the groups Z1, Z2 and Z3 have the same structure "R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e -".

[0080] According to the present invention, in the compounds of formula (I) (or in the preferred compounds of formula (I) as defined herein), the branched or unbranched C 1-10 Fluoroalkyl R i It preferably contains a total of 2 to 15, more preferably a total of 3 to 10, fluorine atoms and / or is preferably unbranched (linear). More preferred and more specific definitions of this group are further defined below.

[0081] In the compounds of formula (I), X is preferably a metal-free monovalent cation, more preferably selected from the group consisting of a proton and a group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-6 Alkyl, preferably branched or unbranched C 1-4 More preferably, X is a proton or ammonium (NR 4 + ).

[0082] In the compounds of formula (I), the anionic polar groups Y1 and / or Y2 are preferably selected from the group consisting of: COO - 、-SO 3 - 、-(O)SO 3 - ,-PO 3 2- and-(O)PO 3 2- Particularly preferably, the anionic polar groups Y1 and / or Y2 are sulfonate groups (-SO 3 - ). In a particularly preferred variant of the compounds of formula (I), Y1 is sulfonate and Y2 is hydrogen.

[0083] In the composition of the invention, the polyalkoxy and / or polyalkyleneoxy groups in the at least one nonionic compound (B) preferably contain at least 5 alkoxy and / or alkyleneoxy groups, respectively.

[0084] The compounds of formula (I) themselves and methods for their preparation are described, for example, in document WO 2010 / 149262 A1.

[0085] Preferred is a composition of the present invention comprising:

[0086] (A) an ionic compound of formula (I) (or a preferred compound of formula (I) as defined above) as a primary surfactant,

[0087] and

[0088] (B) at least one nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups as a secondary surfactant selected from the group consisting of:

[0089] (B1) Compound of formula (II)

[0090] R 5 -[OR 6 ] l -OR 18 (II)

[0091] in

[0092] R 5 It is branched or unbranched, preferably branched C 6-12 fluoroalkyl, or preferably an unbranched or branched, preferably branched, C 6-12 Fluoroalkenyl,

[0093] and it preferably contains a total of 12 to 20 fluorine atoms;

[0094] R 6 Is branched or unbranched C 2-6 Alkylene, preferably branched or unbranched C 2-4 Alkylene, more preferably unbranched C 2-3 Alkylene,

[0095] R 18 is hydrogen or branched or unbranched C 1-4 Alkyl, preferably methyl,

[0096] and

[0097] l is an integer in the range of 5 to 30, preferably in the range of 6 to 25;

[0098] (B2) a compound of formula (III),

[0099] H 3 C-(CH 2 ) m -CH 2 -[OR 7 ] n-OR 19 (III)

[0100] in

[0101] R 7 Is branched or unbranched C 2-6 Alkylene, preferably branched or unbranched C 2-4 Alkylene, more preferably unbranched C 2-3 Alkylene,

[0102] R 19 is hydrogen or branched or unbranched C 1-4 Alkyl, preferably methyl,

[0103] m is an integer in the range of 5 to 30, preferably in the range of 6 to 25,

[0104] and

[0105] n is an integer in the range of 5 to 30, preferably in the range of 6 to 25;

[0106] (B3) a compound of formula (IV),

[0107]

[0108] in

[0109] R 17 Is branched or unbranched C 2-6 Alkylene, preferably branched or unbranched C 2-4 Alkylene, more preferably unbranched C 2-3 Alkylene,

[0110] and

[0111] o is an integer in the range of 5 to 30, preferably in the range of 6 to 25;

[0112] (B4) a compound of formula (V),

[0113]

[0114] in

[0115] R 8 , R 13 and R 14 are independently hydrogen or methyl, preferably R 8 , R 13 and R 14 All are hydrogen,

[0116] R 9 , R 11 and R 12 Each independently of one another is a branched or unbranched C2-6 Alkylene, preferably branched or unbranched C 2-4 Alkylene, more preferably unbranched C 2-3 Alkylene,

[0117] R 10 Is branched or unbranched C 1-4 Alkyl, preferably ethyl,

[0118] and

[0119] p, q and r are each independently an integer in the range of 2 to 25;

[0120] and

[0121] (B5) a compound of formula (VI),

[0122] (H 3 C) 3 Si-OR 15 -O-Si(CH 3 ) 3 (VI)

[0123] in

[0124] R 15 It is composed of:

[0125] The number of repeating units of formula (VII) is in the range of 1 to 100, preferably in the range of 1 to 50:

[0126] -[Si(CH 3 ) 2 -O]-(VII),

[0127] and

[0128] The number of repeating units of formula (VIII) is in the range of 1 to 100, preferably in the range of 1 to 50:

[0129] -[Si(CH 3 )(R 16 )-O]-(VIII),

[0130] Where R 16 is a group containing one or more ethylene glycol (i.e. 1,2-ethylenedioxy) groups and / or one or more propylene glycol (i.e. 1,3-propylenedioxy) groups,

[0131] And wherein the repeating unit of formula (VII) and the repeating unit of formula (VIII) are arranged as follows:

[0132] - randomly arranged, or

[0133] - are arranged in randomly alternating blocks which comprise in each case two or more repeating units of the formula (VII) or of the formula (VIII) per block.

[0134] In the compositions of the invention, one or more ionic compounds of formula (I) may be combined (e.g. mixed) with one or more non-ionic compounds of formula (II), (III), (IV), (V) and / or (VI). Preferred are compositions of the invention in which only one ionic compound (I) is combined with one non-ionic compound, i.e. with a compound of formula (II) or with a compound of formula (III) or with a compound of formula (IV) or with a compound of formula (V) or with a compound of formula (VI).

[0135] Compounds of formula (II), (III), (IV), (V) and (VI) and methods for their production are known in the art, and the corresponding compounds can be purchased commercially, for example, as surfactants. Compounds of formula (II) and methods for the synthesis of these compounds can be found in documents JPS5064208A, JPS50101306A, JPS50101307A and JPS5952520. A preferred compound of formula IV is polyethylene glycol mono(tristyrylphenyl)ether ( RN 99734-09-5). A preferred compound of formula (V) is ethoxylated trimethylolpropane triacrylate ( RN 28961-43-5).

[0136] In the compounds of formula (VI), where more than one ethylene glycol group is present in R 16 In the case where more than one propylene glycol group is present in R 16 In the case of the above, they are preferably linked together and form a polypropylene glycol group. The compound of formula (VI) is commercially available, for example, from the company Shin Etsu (JP) as a side chain polyether-modified polysiloxane. The preferred compound of formula V is sold by Shin Etsu under the name "KF351A". The compound "KF351" contains a polyalkyleneoxy group of formula (IX) as a substituent R 16 :

[0137] R a -(C 2 H 4 O)s(C 3 H 6 O) t -R b (IX)

[0138] Compound KF351 further has a kinematic viscosity at 25° C. of 65 to 75 mm / s, which is preferably measured using a Hoeppler falling ball viscometer according to DIN 53015: 2001-02. Compound KF35 is further characterized by a specific gravity at 25° C. of 1.0 to 1.10, preferably 1.06 (relative to water). Compound KF351 is further characterized by a hydrophile-lipophile balance (HLB) value in the range of 10 to 20, preferably in the range of 10 to 15, more preferably 12, which is determined according to the method of Griffin (see Griffin, WC: “Classification of surface active agents by HLB”, J. Soc. Cosmet. Chem. 1, 1949).

[0139] Preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention) comprising:

[0140] (A) an ionic compound of formula (I) as defined above as a primary surfactant, wherein

[0141] The groups Z1, Z2 and Z3 are each independently of one another a group having the structure R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e - a group, wherein R i , A, R 1 , R 2 , R 3 , R 4 , c, d and e have the meanings or preferred meanings as described above,

[0142] and / or (preferably and)

[0143] (B) at least one nonionic compound of formula (II) as defined above as secondary surfactant.

[0144] In the experiments of the present invention, it has been found that the compositions of the present invention comprising an ionic compound of formula (I) as a primary surfactant and at least one non-ionic compound of formula (II) as defined above (or at least one preferred non-ionic compound of formula (II) as defined herein) as a secondary surfactant have particularly beneficial properties in cleaning or washing products, especially products comprising a substrate, more particularly a semiconductor substrate, and a patterned material supported thereon having a line-space structure with a line width equal to or less than 50 nm, and have particularly beneficial properties in reducing defects on such products. It has also been found in the experiments of the present invention that the compositions of the present invention comprising an ionic compound of formula (I) as a primary surfactant and at least one non-ionic compound of formula (II) as defined above (or at least one preferred formula (II) non-ionic compound as defined herein) as a secondary surfactant exhibit particularly excellent storage stability (shelf life) over a long period of time, for example, over 6 months or longer, preferably over 12 months or longer.

[0145] Preferred is the composition of the present invention as defined herein (or the composition of the present invention described as preferred above or below), wherein in the compound of formula (I), the groups Z1, Z2 and Z3 are each independently of one another an alkyl-fluoroalkyl ether group, which is preferably:

[0146] - having a total of 4 to 50, more preferably 5 to 20, more preferably 6 to 10 carbon atoms,

[0147] and

[0148] - having a total of 2 to 15, more preferably 3 to 10 fluorine atoms,

[0149] and / or preferably

[0150] - bonded via its alkyl group to an oxygen atom adjacent to one or more carboxyl groups of the compound of formula I.

[0151] A preferred example of such a compound of formula (I) as described herein is the compound of formula (Ia) (see below), wherein the alkyl-fluoroalkyl ether group has the structure F 3 C-CF 2 -CH 2 -O-CH 2 -CH(C 2 H 5 )-.

[0152] Preferred is the composition of the present invention as defined herein (or the composition of the present invention described as preferred above or below), wherein in the compound of formula (I),

[0153] X is a metal-free monovalent cation, which is preferably selected from the group consisting of:

[0154] -Proton

[0155] and

[0156] - Group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-6 Alkyl, preferably branched or unbranched C 1-4 alkyl;

[0157] One of Y1 and Y2 is an anionic polar group selected from the group consisting of: -COO - 、-SO 3 - 、-(O)SO 3 - ,-PO 3 2- and-(O)PO 3 2- , preferably sulfonate -SO 3 - , and the other is hydrogen; preferably Y1 is an anionic polar group, and Y2 is hydrogen,

[0158] and

[0159] The radicals Z1, Z2 and Z3 are each independently of one another:

[0160] -With structure R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e -a group, wherein:

[0161] R 1 , R 2 , R 3 and R 4 are independently hydrogen or branched or unbranched C 1-4 alkyl,

[0162] R i Is branched or unbranched C 1-10 Fluoroalkyl,

[0163] c is an integer ranging from 1 to 10,

[0164] d is an integer in the range of 1 to 10,

[0165] and

[0166] e is an integer ranging from 1 to 5.

[0167] Furthermore, preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention), wherein in the compound of formula (I),

[0168] X is selected from the group consisting of:

[0169] -Proton

[0170] and

[0171] - Group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-6 Alkyl, preferably branched or unbranched C 1-4 Alkyl; more preferably NR 4 + Yes NH 4 + ,

[0172] One of Y1 and Y2 is a sulfonate group -SO 3 - , and the other is hydrogen, preferably Y1 is sulfonate and Y2 is hydrogen,

[0173] The radicals Z1, Z2 and Z3 are each independently of one another:

[0174] -With structure F 3 C(CF 2 ) a (CH 2 ) b {-O[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d} e -a group, wherein:

[0175] R 1 , R 2 , R 3 and R 4 are independently hydrogen or branched or unbranched C 1-4 Alkyl, preferably C 1-2 alkyl,

[0176] a is an integer in the range of 0 to 2, preferably a is 1 or 2,

[0177] b is an integer in the range of 1 to 6, preferably b is 1 or 2,

[0178] c is an integer in the range of 1 to 10, preferably c is 1 or 2,

[0179] d is an integer in the range of 1 to 10, preferably d is 1 or 2,

[0180] and

[0181] e is an integer in the range of 1 to 5, preferably e is 1,

[0182] And preferably all the groups Z1, Z2 and Z3 have the same structure.

[0183] Furthermore, particularly preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention), wherein in the compound of formula (I):

[0184] X is selected from the group consisting of:

[0185] -Proton

[0186] and

[0187] - Group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-6 Alkyl, preferably branched or unbranched C 1-4 Alkyl; more preferably NR 4 + Yes NH 4 + ;

[0188] Y1 is sulfonate, -SO 3 - ,

[0189] Y2 is hydrogen,

[0190] and all radicals Z1, Z2 and Z3 have the same structure and are in each case of the formula F 3 C-CF 2 -CH 2 -O-CH 2 -CH(C 2 H 5 )-group.

[0191] Particularly preferred are also compositions of the invention as defined herein (or described above or below as preferred compositions of the invention), wherein the compound of formula (I) is a compound of formula (Ia):

[0192]

[0193] wherein X is selected from the group consisting of: a proton and a group NR 4+ , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-6 Alkyl, preferably branched or unbranched C 1-4 Alkyl; more preferably NR 4 + Yes NH 4 + .

[0194] Furthermore, preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention), wherein the compound of formula (II) is selected from the group consisting of:

[0195] - Compound of formula (IIa):

[0196]

[0197] in

[0198] R 6 , R 18 and l have the above meanings or preferred meanings (as defined above for formula (II)),

[0199] - Compounds of formula (IIb):

[0200]

[0201] in

[0202] R 6 , R 18 and l have the above meanings or preferred meanings (as defined above for formula (II)), and

[0203] - A mixture thereof.

[0204] Particularly preferred are compositions according to the invention comprising: (A) a compound of formula (I), preferably a preferred compound of formula (I) as defined above, as a primary surfactant, and (B) one or more (preferably one) compounds of formula (IIa) and / or one or more (preferably one) compounds of formula (IIb) as secondary surfactants.

[0205] A preferred compound of formula (II) is the reaction product of polyethylene glycol ether with the compound 1,1,1,2,4,5,5,5-octafluoro-3-(1,1,1,2,3,3,3-heptafluoro-2-propyl)-4-(trifluoromethyl)-2-pentene (see, for example, JPS5064208A, JPS50101306A, JPS50101307A and / or JPS5952520), which can be used as a polyol from Neos (JP) 212M commercially available.

[0206] Since aqueous compositions are preferred for the intended use as defect reduction cleaning solutions for semiconductor substrates, preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention) comprising as further components:

[0207] (C) Water, preferably deionized water.

[0208] As described above, it was also found in the experiments of the present invention that the secondary nonionic surfactant (B) according to the present invention, especially the nonionic compound of formula (II) (including particularly preferred compounds of formula (IIa) and formula (IIb)) beneficially regulates the degree of interaction between the primary (ionic) surfactant (A) and the patterned material layer (especially photoresist) having a line-space structure with a line width equal to or less than 50 nm, which improves the solubility and / or colloidal stability of the primary ionic surfactant (A) in water as a carrier solvent, and minimizes the particle adhesion on the surface of the patterned material layer and / or reduces the redeposition of such particles on the surface.

[0209] Also preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention), preferably compositions comprising at least one nonionic compound of formula (II) as secondary surfactant, wherein:

[0210] - the mass ratio between the compound of formula (I) and the compound of formula (II) (including the compound of formula (IIa) and / or the compound of formula (IIb) when present) present in the composition is in the range of 1:4 to 1:1, preferably in the range of 1:3 to 3:4,

[0211] and / or

[0212] - The sum of the following amounts present in the composition:

[0213] - the total amount of compounds of formula (I) and

[0214] -The total amount of the compound of formula (II)

[0215] It is in the range of 0.01 wt% to 0.5 wt%, preferably in the range of 0.02 wt% to 0.25 wt%, more preferably in the range of 0.05 wt% to 0.12 wt%, based on the total weight of the composition.

[0216] In the experiments of the present invention, it was found that the composition of the present invention having the preferred mass ratio between the compound of formula (I) and the compound of formula (II) (preferably the compound of formula (IIa)) present in the composition as defined above has particularly beneficial properties in cleaning or washing products, especially products comprising a substrate, more especially a semiconductor substrate and a patterned material supported thereon having a line-space structure with a line width equal to or less than 50 nm, and has particularly beneficial properties in reducing defects on the product.

[0217] It has also been found in the experiments of the present invention that the composition of the present invention having the preferred mass ratio and total amount (concentration) of the compound of formula (I) and the compound of formula (II) (preferably the compound of formula (IIa) and / or the compound of formula (IIb)) present in the composition as defined above shows a preferred balance on a substrate (e.g. a semiconductor substrate) on which a patterned material having a line-space structure with a line width equal to or lower than 50 nm is supported, this balance being sufficient wettability and sufficiently low surface tension on the one hand and sufficiently low (if any) micelle formation in the composition and / or residue formation on the substrate on the other hand. The formation of micelles in the composition and / or residue formation on the substrate will have an adverse effect on the structure of the patterned material and the subsequent functionality of the resulting product.

[0218] Also preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention), preferably aqueous compositions, which preferably comprise as secondary surfactant at least one nonionic surfactant of formula (II) wherein:

[0219] - the equilibrium surface tension of the composition is less than 35 mN / m, preferably less than 30 mN / m, more preferably less than 28 mN / m, even more preferably less than 25 mN / m, which is preferably measured by the plate method according to DIN 53914: 1997-07 standard at 25° C. with a Kruess surface tensiometer K100,

[0220] and / or

[0221] - The pH of the composition is in the range of 4.0 to 11.0, preferably in the range of 7.0 to 11.0, more preferably in the range of 8.0 to 10.0, even more preferably in the range of 8.0 to 9.6.

[0222] In the experiments of the present invention, it was found that the aqueous composition of the present invention, in particular the aqueous composition comprising the compound of formula (I), preferably the preferred compound of formula (I) as described above and one or more (preferably one) compounds of formula (IIa) and / or compounds of formula (IIb), is particularly stable in an alkaline environment, for example in an environment with a pH of 9-12 or a pH of 9.5-11. The stability of the composition of the present invention in the above alkaline environment is advantageous because particles can usually be best removed from substrates (from conventional processes carried out in the art) in alkaline media, the substrates supporting thereon patterned materials having line-space structures with a line width equal to or less than 50 nm. Therefore, the common methods for cleaning or washing products comprising substrates, preferably semiconductor substrates, are usually carried out with alkaline media, for example because in an alkaline environment, the zeta potential or charge of the particles to be removed supports a repulsive effect, which helps to remove these particles.

[0223] It has also been found that compositions of the invention having a pH in the range of 8.0 to 10.0, preferably in the range of 8.0 to 9.6, are particularly stable over long periods of time and are therefore most suitable where storage stability is optimized. The pH of the compositions of the invention may be adjusted by methods known in the art, for example by adding a suitable amount of a weak acid or weak base, preferably with a low content of metal ions, preferably free of metal ions. A preferred base for adjusting the pH of the compositions of the invention is ammonium hydroxide.

[0224] Also preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention) comprising or consisting of the following components:

[0225] (A) an ionic compound of formula (I) (as defined above, or a preferred compound of formula (I) as defined above) as a primary surfactant,

[0226] (B) at least one nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups (as defined above, or a preferred nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups as defined above), preferably at least one compound of formula (II) (as defined above), as a secondary surfactant,

[0227] (C) Water (as defined above),

[0228] and

[0229] (D) one or more solubilizing agents, preferably one or more partial ethers of alkylene glycols (hydrocarbon glycols) containing a total of 3 to 6 carbon atoms (i.e., at least one hydroxyl group of such partial ethers is a free hydroxyl group), wherein the alkyl group contains a total of 1 to 4 carbon atoms, more preferably one or more partial ethers of ethylene glycol or propylene glycol, in each case whose alkyl group contains a total of 1 to 4 carbon atoms; more preferably the solubilizing agent is or contains 1-methoxy-2-propanol.

[0230] In preferred compositions of the present invention, preferably as described above, the sum of the following amounts is present in the composition:

[0231] - the total amount of the compound of formula (I) (component (A)) and

[0232] - a total amount of at least one nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups, preferably at least one compound of formula (II) (component (B))

[0233] 0.01 wt % to 0.5 wt %, preferably 0.02 wt % to 0.25 wt %, more preferably 0.05 wt % to 0.1 wt %, based on the total weight of the composition; and

[0234] The total amount of the solubilizer(s) (component (D)) in the composition is in the range of 0.01 wt % to 0.5 wt %, preferably in the range of 0.02 wt % to 0.25 wt %, more preferably in the range of 0.05 wt % to 0.1 wt %, based on the total weight of the composition.

[0235] Also preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention), wherein:

[0236] - the total amount of components (A), (B), (C) and (D), preferably the total amount of components (A), (B) and (C), based on the total weight of the composition, exceeds 90% by weight, preferably exceeds 95% by weight, even more preferably exceeds 98% by weight,

[0237] and / or

[0238] - The pH of the composition is in the range of 7.0 to 11.0, preferably in the range of 8.0 to 10.0, more preferably in the range of 8.0 to 9.6.

[0239] In addition to the above-described components (A) to (D), the preferred compositions of the present invention preferably contain a weak acid or a weak base only in an amount required to adjust the pH of the composition to the values ​​or preferred values ​​described herein.

[0240] To measure the equilibrium surface tension by the plate method according to DIN 53914: 1997-07 (see above), a thin plate with an area of ​​usually several square centimeters is used. The plate is usually made of platinum with a high surface energy to ensure complete wetting. The force F on the plate caused by wetting is measured with a surface tensiometer (or microbalance), which is used to calculate the equilibrium surface tension according to the Wilhelmy equation:

[0241]

[0242] where l is the wetted perimeter of the Wilhelmy plate and θ is the equilibrium contact angle between the liquid phase and the plate. This equilibrium contact angle is different from the contact angle used to calculate the maximum stress σ between small features (e.g., of photoresists) caused by capillary forces (see above).

[0243] The contact angle is generally the angle measured for a liquid in contact with a solid surface via a conventional liquid-vapor interface. It is quantified by the Young equation, which is well known in the art, for the wettability of a liquid to a solid surface. A given solid, liquid, and vapor system at a given temperature and pressure has a unique equilibrium contact angle. The equilibrium contact angle reflects the relative strength of the interaction between liquid, solid, and vapor molecules.

[0244] It was also found in the experiments of the present invention that the compositions of the present invention having the preferred equilibrium surface tension described above show a beneficial spreading ability, which indicates an excellent and fast cleaning or washing operation on the product. "Excellent spreading ability" is preferably characterized by the following parameters: a low equilibrium contact angle on the product, especially a product comprising a substrate, more especially a semiconductor substrate and a patterned material having a line-space structure with a line width equal to or less than 50 nm supported thereon (e.g., a photoresist supported on a semiconductor wafer), i.e., an equilibrium contact angle in the range of 0° to 25°, preferably in the range of 0° to 20°, the equilibrium contact angle preferably being determined according to the DIN 53914: 1997-07 standard. The equilibrium surface tension can be adjusted by a person skilled in the art according to methods known in the art.

[0245] The lower the equilibrium surface tension of the composition, the lower the capillary force to prevent or reduce pattern collapse (e.g., Namatsu et al., Appl. Phys. Let. 66 (20), 1995, supra). An additional advantage of the composition of the present invention having a specific equilibrium surface tension and / or its use is that it is extremely effective in penetrating and cleaning a patterned material layer having a line-space structure (pattern) at the nm level.

[0246] Particularly preferred are compositions of the invention as defined herein (or described above or below as preferred compositions of the invention) comprising:

[0247] (A) an ionic compound of formula (I) as a primary surfactant,

[0248] in

[0249] X is selected from the group consisting of: a proton and a group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-6 Alkyl, preferably branched or unbranched C 1-4 Alkyl; more preferably NR 4 + Yes NH 4 + ,

[0250] Y1 is sulfonate, -SO 3 - ,

[0251] Y2 is hydrogen,

[0252] and

[0253] All radicals Z1, Z2 and Z3 have the same structure and are in each case of the formula F 3 C-CF 2 -CH 2 -O-CH 2 -CH(C 2 H 5 )-group,

[0254] and

[0255] (B) at least one nonionic compound of formula (IIa) as a secondary surfactant,

[0256]

[0257] in

[0258] R 6 Is branched or unbranched C 2-4 Alkylene, preferably unbranched C 2-3 Alkylene,

[0259] R 18 is hydrogen or branched or unbranched C 1-4 Alkyl, preferably methyl,

[0260] and

[0261] l is an integer in the range of 5 to 30, preferably in the range of 6 to 25,

[0262] and / or (i.e. a mixture comprising at least one compound of formula (IIa) and at least one compound of formula (IIb))

[0263] At least one compound of formula (IIb):

[0264]

[0265] in

[0266] R 6 Is branched or unbranched C 2-4 Alkylene, preferably unbranched C 2-3 Alkylene,

[0267] R 18 is hydrogen or branched or unbranched C 1-4 Alkyl, preferably methyl,

[0268] and

[0269] l is an integer in the range of 5 to 30, preferably in the range of 6 to 25,

[0270] and

[0271] (C) Water,

[0272] wherein the pH of the composition is in the range of 7.0 to 11.0, preferably in the range of 8.0 to 10.0, more preferably in the range of 8.0 to 9.6,

[0273] And preferably:

[0274] - The sum of the following amounts present in the composition:

[0275] - the total amount of compounds of formula (I) and

[0276] -The total amount of the compound of formula (II)

[0277] It is in the range of 0.01 wt% to 0.5 wt%, preferably in the range of 0.02 wt% to 0.25 wt%, more preferably in the range of 0.05 wt% to 0.1 wt%, based on the total weight of the composition.

[0278] The present invention also relates to the use of a composition of the invention as defined herein for a cleaning or washing product (or to the use of a composition of the invention described herein as preferred), preferably a product comprising a substrate and a patterned material supported thereon having a line-space structure with a line width equal to or lower than 50 nm, such that preferably:

[0279] - prevent or reduce pattern collapse,

[0280] - Reduce line edge roughness,

[0281] - prevent or remove watermark defects,

[0282] - prevent or reduce photoresist swelling,

[0283] -Prevent or reduce spot defects,

[0284] and / or

[0285] -Remove particles.

[0286] Generally speaking, all aspects of the invention described in the context of the compositions of the invention for use in cleaning or cleaning products apply mutatis mutandis to the use of the cleaning compositions of the invention as defined above and below, and vice versa.

[0287] The cleaned or rinsed products for use according to the invention are preferably products used in the semiconductor industry.

[0288] The presence of the aforementioned defects or effects will have a negative impact on the performance of the resulting product, especially on devices such as integrated circuit devices, optical devices, micromechanical or mechanical precision devices, and accordingly, the present invention (which helps to avoid these defects or effects) has high industrial value.

[0289] Thus, preferred is the use of a composition of the invention as defined herein (or described herein as a preferred use of the invention) wherein:

[0290] - the cleaning or rinsing is part of a process for producing integrated circuit devices, optical devices, micromechanical or mechanical precision devices,

[0291] and / or

[0292] - The substrate is a semiconductor substrate, preferably a semiconductor wafer.

[0293] Also preferred is the use of a composition of the invention as defined herein (or described herein as a preferred use of the invention) wherein:

[0294] - the patterned material layer having a line-space structure with a line width equal to or lower than 50 nm is selected from the group consisting of: a patterned developed photoresist layer, a patterned isolation material layer, a patterned multi-stacked material layer and a patterned dielectric material layer,

[0295] and / or

[0296] - the patterned material layer has an aspect ratio greater than 2, preferably greater than 3, for the photoresist structure and / or for the patterned multi-stacked line / space structure,

[0297] and / or

[0298] The patterned material has a line-space structure with a line width equal to or lower than 32 nm, preferably equal to or lower than 22 nm.

[0299] Patterned developed photoresist layers, patterned isolation material layers, patterned multi-stack material layers, and patterned dielectric material layers are particularly susceptible to pattern collapse, low line edge roughness, and photoresist swelling. Avoiding these negative effects can improve device performance and production output because the number of failed devices is significantly reduced.

[0300] Preferred is the use according to the invention of a composition as defined above (or as defined above as preferred), wherein the patterned material layer has an aspect ratio greater than 10 for non-photoresist structures and an aspect ratio greater than 2, preferably greater than 3 for photoresist structures. Material layers having an aspect ratio greater than 10 for non-photoresist structures and greater than 2, preferably greater than 3 for photoresist structures are particularly prone to pattern collapse during cleaning or washing, and are therefore preferably cleaned and washed with a composition as described above, preferably with a composition as described above having an equilibrium surface tension of less than 35 mN / m, preferably less than 30 mN / m, more preferably less than 28 mN / m, even more preferably less than 25 mN / m, the equilibrium surface tension preferably being measured at the critical micelle concentration. Such compositions have the advantage of being particularly effective in reducing or avoiding pattern collapse.

[0301] In particular, preferred is the use according to the invention of a composition as defined above (or as defined above as preferred), wherein the patterned material layer has a line-space structure with a line width equal to or lower than 32 nm, preferably equal to or lower than 22 nm. A patterned material layer with a line-space structure with a line width equal to or lower than 32 nm, preferably equal to or lower than 22 nm, is particularly prone to pattern collapse during cleaning or washing, and is therefore preferably cleaned and washed with a composition as described above, preferably with a composition as described above having an equilibrium surface tension of less than 35 mN / m, preferably less than 30 mN / m, more preferably less than 28 mN / m, even more preferably less than 25 mN / m, the equilibrium surface tension preferably being measured at the critical micelle concentration.

[0302] The present invention also relates to a method for producing a cleaned or rinsed product, the product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or less than 50 nm, the method comprising the steps of:

[0303] - preparing or providing a product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or less than 50 nm,

[0304] - preparing or providing a composition according to the invention as defined above (or a preferred composition according to the invention as defined above),

[0305] and

[0306] - Cleansing or washing the product with the composition to obtain a cleansed or washed product.

[0307] Generally speaking, all aspects of the invention discussed in the context of the inventive composition for a cleaning or washing product and / or the inventive use of such a composition apply mutatis mutandis to the inventive method for producing a cleaned or washed product as defined herein, and vice versa.

[0308] Preferred is the process of the invention as defined herein, further comprising the steps of:

[0309] - providing a substrate having an immersion photoresist layer, an EUV photoresist layer or an electron beam photoresist layer,

[0310] - exposing the photoresist layer to actinic radiation through a photomask in the presence or absence of an immersion liquid,

[0311] - developing the exposed photoresist layer with a developer solution to obtain a pattern having a line-space structure with a line width equal to or lower than 50 nm, so as to produce a product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or lower than 50 nm,

[0312] - cleaning or washing the product with the composition to obtain a cleaned or washed product,

[0313] and optionally,

[0314] - Drying of the cleaned or washed product is preferably carried out by spin drying or by a drying process. Example:

[0315] The following examples are intended to further explain and illustrate the present invention but are not intended to limit the scope thereof.

[0316] Example 1: Preparation of test composition

[0317] The following compositions I1, I1a and I2 according to the present invention and compositions C1 and C2 as comparative compositions not according to the present invention (hereinafter collectively referred to as "test compositions") were prepared by conventional mixing of the components shown in Table 1a. After mixing, the pH of the compositions was adjusted as required by adding a dilute aqueous ammonia solution. In the compositions shown in Table 1a and Table 1b, the compound of formula (I) used was wherein X is NH 4 + , Y1 is sulfonate -SO 3 -, Y2 is hydrogen, and the groups Z1, Z2 and Z3 have the same structure and are in each case of the formula F 3 C-CF 2 -CH 2 -O-CH 2 -CH(C 2 H 5 )-group.

[0318] In the compositions shown in Table 1a and Table 1b, the compound of formula (II) is 212M (see above).

[0319] In the compositions shown in Table 1b, the compound of formula (III) is TO8, a C13 oxo alcohol ethoxylate detergent commercially available from BASF SE.

[0320] In the compositions shown in Table 1b, the compound of formula (IV) is polyethylene glycol mono(tristyrylphenyl) ether ( RN 99734-09-5).

[0321] In the compositions shown in Table 1b, the compound of formula (V) is an average M n ≈912 trimethylolpropane ethoxylate triacrylate ( RN 28961-43-5).

[0322] In the compositions shown in Table 1a and Table 1b, the compound of formula (VI) is KF351 A (see above).

[0323] Table 1a: Compositions of the invention and comparative compositions

[0324]

[0325] na: No data points available

[0326] The following compositions I1b, I2a, I3, I4 and I5 according to the present invention, and composition C3 as a comparative composition not according to the present invention (also collectively referred to as "test compositions" hereinafter) were prepared by conventionally mixing the components shown in Table 1b. After mixing, the pH of the composition was adjusted as needed by adding a dilute aqueous ammonia solution.

[0327] Table 1b: Compositions of the invention and comparative compositions

[0328]

[0329] Example 2: Detection of critical micelle concentration (CMC)

[0330] Using Kruess surface tensiometer K100, CMC is determined by measuring the equilibrium surface tension of a series of surfactant aqueous solutions with different concentrations according to the plate method. The resulting chart usually has two different regions. Below the CMC, the equilibrium surface tension depends linearly on the logarithm of the surfactant concentration over a wide range. Above the CMC, the equilibrium surface tension is more or less independent of the concentration of the surfactant. The data points in the two regions can be fitted statistically by simple linear regression. CMC is the intersection between the two linear regression lines fitted to the data in these regions.

[0331] Example 3: Equilibrium Surface Tension of the Compositions of the Invention

[0332] The equilibrium surface tension of aqueous surfactant solutions was determined by the plate method at 25° C. according to DIN 53914: 1997-07 using a Kruess surface tensiometer K100.

[0333] The plate method uses a thin plate, usually a few square centimeters in area. The plate is usually made of platinum with a high surface energy to ensure complete wetting. The force F on the plate caused by wetting is measured with a surface tensiometer or microbalance and used to calculate the equilibrium surface tension according to the Wilhelmy equation:

[0334]

[0335] Where l is the wetted perimeter of the Wilhelmy plate and θ is the contact angle between the liquid phase and the plate. These results are listed in Tables 1a and 1b above.

[0336] From the results, it can be seen that the composition of the present invention has an equilibrium surface tension of less than 30 mN / m, and the preferred composition of the present invention has an equilibrium surface tension of less than 28 mN / m. The preferred composition I1 of the present invention has an equilibrium surface tension of less than 25 mN / m.

[0337] Example 4: Storage stability of the composition of the present invention

[0338] The test composition was prepared as described in Example 1 above and stored at 25° C. and 40% relative humidity for 9 weeks. Before (i.e. immediately after preparation of the composition) and after this storage time, the CMC curve of the test composition was analyzed in each case by the surface tension measurement method described in Example 2 above: the equilibrium surface tension was measured on a series (i.e. more than ten) of aqueous surfactant solutions of different concentrations with up to a 100-fold dilution (with deionized water). The results of this test are listed in Table 2 below.

[0339] Table 2: Storage stability of the compositions

[0340]

[0341] From the results of Example 4, it can be seen that the composition I1 of the present invention shows the best storage stability under storage conditions because its equilibrium surface tension does not change (increase) during the storage period. It can also be seen from the experimental results that for the purpose of optimizing storage stability, the most suitable pH of the composition of the present invention is lower than pH 10, preferably equal to or lower than pH 9.6; for the composition of the present invention with a pH equal to or lower than 9.6, it is found that the surfactant contained therein is rarely or not degraded.

[0342] Example 5: Cleaning Performance of Compositions of the Invention and Comparative Compositions as Measured by Critical Dimension

[0343] The Si semiconductor test wafer was coated with a standard positive photoresist and followed a standard sequence of process steps: baking the photoresist, exposing to actinic radiation, and developing the positive photoresist with an aqueous developer solution (containing 2.38 wt % TMAH) to create a line-space / via structure with a line width / via diameter of 40 nm / 70 nm on the wafer surface, as is well known in the art.

[0344] After the development step, without drying the liquid melt pool on the wafer, the line-space structures created on the test wafer were subsequently cleaned with the compositions I1, I1a, I1b, I2, I2a, I3, I4 and I5 of the present invention and with the comparative compositions C1, C2 and C3 (all compositions as defined in Example 1, all experiments were performed on separate semiconductor wafers for each test composition), and then each test composition (as a cleaning solution) was sprayed onto the test wafer surface for 5 seconds at a flow rate of 10 ml / sec. For further comparison, these line-space structures were also cleaned under the same conditions (after the development step) with a standard defect reduction cleaning aqueous solution of the prior art, which contained an anionic unbranched (linear) fluoroalkyl compound as the sole surfactant and had a pH in the range of 9.4 to 9.7 and a surface tension in the range of 25 to 30 mN / m (hereinafter referred to as "composition POR").

[0345] After cleaning with the composition described above, the critical dimension (CD) "line width / via diameter" was measured by critical dimension scanning electron microscopy ("CD SEM"; KLA 8100XP of KLA Tencor, USA) by averaging 30 corresponding measurements after cleaning in each case, the measurement being made in dense areas (i.e., repeating pattern arrangement in X and Y dimensions), semi-dense areas (i.e., repeating pattern arrangement only in X or Y dimensions) and isolated areas (i.e., each individual pattern is isolated from each other), and the critical dimension is defined as the critical dimension relevant to this experiment. The critical dimension generally describes the size of the pattern present on the semiconductor wafer, such as the line / space width or the via / hole diameter, and more particularly the smallest dimension shown on the semiconductor wafer.

[0346] After cleaning with the inventive compositions I1, I1a, I1b, I2, I2a, I3, I4 and I5 and the comparative compositions C1, C2 and C3 and the composition POR, the critical dimensions measured by the above method were collected and compared using the CD software of the scanning electron microscope. Subsequently, the critical dimension differences between the inventive compositions I1, I1a, I1b, I2, I3, I4 and I5 on the one hand and the comparative compositions C1, C2 and C3 and on the other hand and the composition POR were calculated using the software and presented in the format of "maximum critical dimension approach deviation compared to the composition POR" (i.e., the maximum CD deviation between the wafer cleaned with the test composition and the wafer cleaned with the standard cleaning solution composition POR) in the area of ​​interest (the dense, semi-dense or separated area shown in Tables 3a and 3b below). A "maximum critical dimension approach deviation" value equal to or less than 2 nm relative to the corresponding critical dimension value measured with the standard composition POR indicates a preferred cleaning effect achieved with the test composition. The value of "Maximum critical dimension approach deviation" should be as low as possible, and a value of 2 nm is a preferred upper threshold value that is acceptable for further processing, where the performance of the final device or product will not be limited due to, for example, poor cleaning or washing results. The results of this test are listed in Table 3a and Table 3b below.

[0347] Table 3a: Critical Dimension Measurements - Part A

[0348]

[0349] Table 3b: Critical Dimension Measurements - Part B

[0350]

[0351] From the results of Example 5, it can be concluded that the compositions of the present invention (comprising an ionic compound of formula (I) as a primary surfactant and at least one nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups as a secondary surfactant, i.e., compositions I1, I1a, I1b, I2, I2a, I3, I4 or I5) show better cleaning results (possibly due to a higher defect reduction potential) than the comparative compositions, wherein the comparative compositions comprise only an ionic compound of formula (I) (i.e., comparative composition C1) or only a nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups (i.e., comparative composition C2), thereby illustrating the synergistic effect of the compositions of the present invention comprising both a primary surfactant and a secondary surfactant as described herein. The most unfavorable results in this test model were obtained in the case of comparative test composition C3 comprising choline hydroxide as a primary surfactant and a compound of formula III as a secondary surfactant. Comparative test composition C3 obviously fails to meet the success criteria of the test model of the present invention (a "maximum critical dimension approach deviation" value equal to or less than 2nm relative to the corresponding critical dimension value measured using the standard composition POR), and is therefore not considered to be suitable for cleaning or rinsing a product comprising a substrate and a patterned material layer supported thereon having a line-space structure with a line width equal to or less than 50nm.

[0352] The best results were achieved with composition I1 according to the invention, which showed the best cleaning results in the test setting.

[0353] Example 6: Liquid Particle (Micelle) Content of Composition

[0354] Compositions I1 (the present invention) and C1 (comparative composition) were prepared as described in Example 1 above. The two compositions were filtered for 24 hours using a HDPE (high density polyethylene) filter material (0.02 μm pore size, Entegris). After filtration, the liquid particle content of the two compositions was detected by light scattering using a Rion KL 27 particle counter (Rion Co., Ltd. JP), as described in, for example, K. Kondo et al., "Measurement of Particles in Liquid Materials Using the Light Scattering Method", "Interfacial Nano Electrochemistry, March 2013" conference proceedings.

[0355] Generally speaking, light scattering occurs when a sample introduced from the nozzle of a particle counting instrument is illuminated with light and then the particles pass through the light. The scattered light is detected by a photodetector and converted into an analyzable electrical signal: the size of the electrical signal represents the particle size, and the frequency of the scattered light detection represents the particle count (the number of particles).

[0356] The data were sampled in each case by averaging three single measurements for each test composition. The results of this experiment are listed in Table 4 below.

[0357] Table 4: Liquid Particle Counts in Test Compositions

[0358]

[0359] The term "out of measurement range" in Table 4 means that the number of particles measured by the particle counting instrument is too high to be counted in the experimental setup.

[0360] As can be seen from the data in Table 4, the composition of the present invention contains significantly fewer particles than the comparative composition not of the present invention. These particles mainly contain partially soluble surfactant aggregates ("micelles"), which can pass through the pores of the filter material when squeezed. Therefore, in this experiment, solid (hard) particles are filtered out, but surfactant aggregates cannot be filtered (or to a significantly smaller extent). However, the particles that are not filtered (surfactant aggregates) will have a negative impact on the cleaning or washing effect of the corresponding composition.

[0361] Example 7: Equilibrium contact angle of the composition of the present invention on a product comprising a substrate

[0362] The composition of the present invention, namely composition "I1b" (similar to composition I1 of the example, but having a lower collective concentration of compound of formula (I) and compound of formula (II) of 0.05 weight % based on the total mass of the composition), and comparative composition C1 (not of the present invention) were prepared as described in Example 1.

[0363] A flat semiconductor wafer ("substrate") coated with a conventional unexposed positive photoresist is placed on a horizontal stand of a Kruss drop shape analyzer (DSA 100, Kruss GmbH, Germany) equipped with a light screen when in use. In order to add the test composition, a microliter syringe is placed in the center of the substrate and connected to the micromanipulator of the drop shape analyzer. The micromanipulator is used to carefully adjust the needle tip position of the syringe to above the wafer. The tip of the syringe is positioned a few microns away from the substrate surface to eliminate the impact effect when releasing the small droplet of the test composition. The drop volume is selected to be 2 μl in each case so that the influence of gravity can be ignored. The droplets are recorded using a charge coupled device (CCD) camera and are coated on the substrate according to the specified volume by the precise movement of the syringe of the contact angle instrument, and the equilibrium contact angle is measured immediately after the test composition is coated on the substrate ("0 seconds"), and measured again 10 seconds thereafter. The results of this experiment are listed in Table 5 below.

[0364] Table 5: Equilibrium contact angles of the compositions

[0365]

[0366] As can be seen from the above results in Table 5, the equilibrium contact angle of the composition of the present invention is much smaller than the contact angle of the comparative composition not of the present invention, which indicates that the composition of the present invention has better wettability (i.e., can be better wetted) of the substrate surface (i.e., the photoresist-coated surface of the semiconductor wafer) than the comparative composition not of the present invention. A composition showing good wettability of a substrate can generally achieve better cleaning or washing effects and / or better defect reduction effects on the substrate than a composition showing poor wettability of the substrate.

[0367] Example 8: Cleaning performance of the composition of the present invention and the comparative composition under pattern collapse

[0368] The Si semiconductor test wafer was coated with a standard positive photoresist and followed a standard sequence of process steps: baking the photoresist, exposing to actinic radiation, and developing the positive photoresist with an aqueous developer solution (containing 2.38 wt % TMAH) to create a line-space / via structure with a line width / via diameter of 40 nm / 70 nm on the wafer surface, as is known in the art.

[0369] After the development step, without drying the liquid melt pool on the wafer, the line-space structures created on the test wafer were then cleaned with the compositions I1b, I2a, I3, I4 and I5 of the present invention and with the comparative composition C3 (all compositions as described in Example 1 above, all experiments were performed on separate semiconductor wafers for each test composition), and each test composition was then sprayed (as a cleaning solution) onto the test wafer surface at a flow rate of 10 ml / s for 5 seconds.

[0370] After cleaning with the composition defined above, the test wafers were coated with a thin protective layer of platinum (as known in the art to enhance surface conductivity, the thickness of the platinum layer was about <0.5 nm). Subsequently, 5 test areas of 10 μm each were randomly selected for each test wafer, and each test area was examined by a top-down (or slightly tilted) view scanning electron microscopy (SEM) with a Hitachi SU 8220 scanning electron microscope for the number of pattern collapses of the previously created line-space / via structure (see above). The number of collapsed patterns from the 5 test areas on the test wafer was counted, and the average number obtained was rounded and recorded as the result (per test wafer).

[0371] The results of this experiment are listed in Table 6 below.

[0372] Table 6: Inspection of pattern collapse of line-space structures after cleaning with the test compositions

[0373]

[0374] From the results of Example 8 shown in Table 6 above, it can be seen that the compositions of the present invention (i.e., compositions I1b, I2a, I3, I4 or I5) all show significantly better cleaning results on a patterned material layer having a line width of equal to or less than 50 nm in a line-space structure compared to a comparative composition (i.e., comparative composition C3), wherein the composition of the present invention comprises an ionic compound of formula (I) as a primary surfactant and at least one nonionic compound containing one or more polyalkoxy groups and / or polyalkylene oxides as a secondary surfactant, and the comparative composition comprises an ionic compound not of the present invention (i.e., choline hydroxide) and at least one nonionic compound containing one or more polyalkoxy groups and / or polyalkylene oxides as a secondary surfactant; that is, cleaning with the composition of the present invention results in a significantly lower number of pattern collapses in the cleaned structure than cleaning with the comparative composition.

[0375] In this test method, the compositions I1b, I2a, I3, and I4 of the present invention show particularly excellent cleaning results on patterned material layers having line-space structures with line widths equal to or less than 50 nm, and the number of pattern collapses of the cleaned structures is particularly low. Therefore, the compositions I1b, I2a, I3, and I4 represent preferred compositions of the present invention.

[0376] In this test method, composition I1b of the present invention shows the best cleaning results on patterned material layers having line-space structures with line widths equal to or less than 50 nm, with no pattern collapse of the cleaned structures at all. Therefore, composition I1b represents a particularly preferred composition of the present invention.

Claims

1. A composition for cleaning or washing products, comprising: (A) an ionic compound of formula (I) as a primary surfactant, in X is a metal-free monovalent cation selected from the group consisting of: -Proton and - Group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-6 alkyl; One of Y1 and Y2 is an anionic polar group selected from the group consisting of: -COO - 、-SO 3 - 、-(O)SO 3 - ,-PO 3 2- and-(O)PO 3 2- , and the other is hydrogen, The radicals Z1, Z2 and Z3 are each independently of one another: -With structure R i -{A[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d } e -group, in: R 1 , R 2 , R 3 and R 4 are independently hydrogen or branched or unbranched C 1-4 alkyl, R i Is branched or unbranched C 1-10 Fluoroalkyl, A is oxygen, sulfur and / or -N(H)-, c is an integer ranging from 1 to 10, d is an integer in the range of 1 to 10, e is an integer ranging from 1 to 5, and (B) at least one nonionic compound containing one or more polyalkoxy and / or polyalkyleneoxy groups as a secondary surfactant, the at least one nonionic compound being selected from the group consisting of: (B1) a compound of formula (II), wherein the compound of formula (II) is selected from the group consisting of: - Compound of formula (IIa): in R 6 Is branched or unbranched C 2-6 Alkylene, R 18 is hydrogen or branched or unbranched C 1-4 alkyl, and l is an integer in the range of 5 to 30, - Compounds of formula (IIb): in R 6 Is branched or unbranched C 2-6 Alkylene, R 18 is hydrogen or branched or unbranched C 1-4 Alkyl, and l is an integer in the range of 5 to 30, and - mixtures thereof; (B2) a compound of formula (III), H 3 C-(CH 2 ) m -CH 2 -[O-R 7 ] n -OR 19 (III) in R 7 Is branched or unbranched C 2-6 Alkylene, R 19 is hydrogen or branched or unbranched C 1-4 alkyl, m is an integer in the range of 5 to 30; and n is an integer ranging from 5 to 30; (B3) a compound of formula (IV), in R 17 Is branched or unbranched C 2-6 Alkylene, and o is an integer in the range of 5 to 30, (B4) a compound of formula (V), in R 8 , R 13 and R 14 are each independently hydrogen or methyl, R 9 , R 11 and R 12 Each independently of one another is a branched or unbranched C 2-6 Alkylene, R 10 Is branched or unbranched C 1-4 alkyl, and p, q and r are each independently an integer in the range of 2 to 25, and (B5) a compound of formula (VI), (H 3 C) 3 Si-OR 15 -O-Si(CH 3 ) 3 (VI) in R 15 It is composed of: The number of repeating units of formula (VII) ranges from 1 to 100: -[Si(CH 3 ) 2 -O]-(VII), and The number of repeating units of formula (VIII) ranges from 1 to 100: -[Si(CH 3 )(R 16 )-O]-(VIII), Where R 16 is a group comprising one or more ethylene glycol groups and / or one or more propylene glycol groups, and wherein the repeating units of formula (VII) and the repeating units of formula (VIII) are arranged as follows: - randomly arranged, or - are arranged in randomly alternating blocks which comprise in each case two or more repeating units of the formula (VII) or of the formula (VIII) per block.

2. The composition according to claim 1, comprising: (B1) at least one nonionic compound of formula (II) as a secondary surfactant.

3. The composition according to claim 1, wherein in the compound of formula (I), X is selected from the group consisting of: -Proton and - Group NR 4 + , wherein each R is independently selected from the group consisting of: H and branched or unbranched C 1-4 alkyl, One of Y1 and Y2 is a sulfonate group -SO 3 - , and the other is hydrogen, The radicals Z1, Z2 and Z3 are each independently of one another: -With structure F 3 C(CF 2 ) a (CH 2 ) b {-O[-C(R 1 )(R 2 )-] c [-C(R 3 )(R 4 )-] d } e -group, in: R 1 , R 2 , R 3 and R 4 are independently hydrogen or branched or unbranched C 1-4 alkyl, a is an integer in the range of 0 to 2, b is 1 or 2, c is 1 or 2, d is 1 or 2, and e is 1, And wherein all the groups Z1, Z2 and Z3 have the same structure.

4. The composition according to any one of claims 1 to 3, comprising the following components as further components: (C) Water.

5. The composition according to claim 2, wherein the compound of formula (II) is present in the composition, and - the mass ratio between the compound of formula (I) and the compound of formula (II) present in the composition is in the range of 1:4 to 1:1, and / or - The sum of the following amounts present in the composition: - the total amount of compounds of formula (I) and -The total amount of the compound of formula (II) It is in the range of 0.01 wt% to 0.5 wt% based on the total weight of the composition.

6. A composition according to any one of claims 1 to 3, in: - the equilibrium surface tension of the composition is less than 35 mN / m, measured at 25° C. using a Kruess surface tensiometer K 100 by the plate method according to DIN 53 914:1997-07, and / or - The pH of the composition is in the range of 7.0 to 11.

0.

7. Use of a composition as defined in any one of claims 1 to 6 for cleaning or washing a product, the product being a product comprising a substrate and a patterned material supported thereon, the patterned material having a line-space structure with a line width equal to or lower than 50 nm.

8. The use according to claim 7, in: - the cleaning or rinsing is part of a process for producing integrated circuit devices, optical devices, micromechanical or mechanical precision devices, and / or - The substrate is a semiconductor substrate.

9. The use according to any one of claims 7 to 8, wherein the composition is used for cleaning or washing such that: - prevent or reduce pattern collapse, - Reduce line edge roughness, - prevent or remove watermark defects, - prevent or reduce photoresist swelling, -Prevent or reduce spot defects, and / or -Remove particles.

10. The use according to any one of claims 7 to 8, in: - the patterned material layer having a line-space structure with a line width equal to or lower than 50 nm is selected from the group consisting of: a patterned developed photoresist layer, a patterned isolation material layer, a patterned multi-stacked material layer and a patterned dielectric material layer, and / or - the patterned material layer has an aspect ratio greater than 2 for the photoresist structure and / or for the patterned multi-stacked line / space structure, and / or - The patterned material has a line-space structure with a line width equal to or lower than 32 nm.

11. A method of producing a cleaned or rinsed product, the product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or less than 50 nm, the method The following steps are involved: - preparing or providing a product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or less than 50 nm, - preparing or providing a composition as defined in any one of claims 1 to 6, and - Cleansing or washing the product with the composition to obtain a cleansed or washed product.

12. The method according to claim 11, further comprising: The following steps are involved: - providing a substrate having an immersion photoresist layer, an EUV photoresist layer or an electron beam photoresist layer, - exposing the photoresist layer to actinic radiation through a photomask in the presence or absence of an immersion liquid, - developing the exposed photoresist layer with a developer solution to obtain a pattern having a line-space structure with a line width equal to or lower than 50 nm, so as to produce a product comprising a substrate and a patterned material layer supported thereon, the patterned material layer having a line-space structure with a line width equal to or lower than 50 nm, - cleaning or washing the product with the composition to obtain a cleaned or washed product, and optionally, - Drying of cleaned or washed products.

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