Composition comprising a primary and a secondary surfactant, for cleaning or rinsing a product

Abstract

Described is a composition comprising as primary surfactant an ionic compound comprising one or more fluoroalkyl groups and as secondary surfactant at least one non-ionic compound comprising one or more polyalkyloxy and/or polyalkylenoxy groups, for cleaning or rinsing a product, preferably a product used in the semiconductor industry, and a respective use of said composition. Further described is a method of making a cleaned or rinsed product, preferably a product used in the semiconductor industry, comprising a substrate and supported thereon a patterned material layer having line-space structures with a line width of 50 nm or below, comprising the step of cleaning or rinsing said product with the composition of the invention.

Claims

1. A composition for cleaning or rinsing a product, comprising: a primary surfactant comprising an ionic compound of formula (I), ##STR00009## wherein: X is a cation, one of Y1 and Y2 is an anionic polar group and the other is hydrogen, and each group of Z1, Z2 and Z3 is, independent of each other, a branched or unbranched C.sub.1-10-alkyl group or a group of the structure R.sup.i{A[C(R.sup.1)(R.sup.2)].sub.c[C(R.sup.3)(R.sup.4)].sub.d}.sub.e, wherein: R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are, independent of each other, hydrogen or a branched or unbranched C.sub.1-4-alkyl group, R.sup.i is a branched or unbranched C.sub.1-10-fluoroalkyl group, A is oxygen, sulfur and/or N(H), c is an integer in the range of from 0 to 10, d is an integer in the range of from 0 to 10, e is an integer in the range of from 1 to 5, c and d are not both 0, and at least one of the groups Z1, Z2 or Z3 is a group of the structure R.sup.i{A[C(R.sup.1)(R.sup.2)].sub.c[C(R.sup.3)(R.sup.4)].sub.d}.sub.e; and a secondary surfactant comprising at least one non-ionic compound comprising one or more polyalkyloxy and/or polyalkylenoxy groups selected from the group consisting of a compound of formula (II) selected from the group consisting of a compound of formula (IIa): ##STR00010## and a compound of formula (IIb): ##STR00011## wherein R.sup.6 is a branched or unbranched C.sub.2-6-alkylen group, R.sup.18 is hydrogen or a branched or unbranched C.sub.1-4-alkyl group, and l is an integer in the range of from 5 to 30; a compound of formula (IV), ##STR00012## wherein R.sup.17 is a branched or unbranched C.sub.2-6-alkylen group, and o is an integer in the range of from 5 to 30; a compound of formula (V), ##STR00013## wherein R.sup.8, R.sup.13 and R.sup.14 are each independent of each other, hydrogen or methyl, R.sup.9, R.sup.11 and R.sup.12 are each independent of each other a branched or unbranched C.sub.2-6-alkylen group, R.sup.10 is a branched or unbranched C.sub.1-4-alkyl group, and p, q and r are each independent of each other an integer in the range of from 2 to 25; and a compound of formula (VI),
(H.sub.3C).sub.3SiOR.sup.15OSi(CH.sub.3).sub.3(VI), wherein R.sup.15 consists of a number in the range of from 1 to 100 of repeating units of formula (VII):
[Si(CH.sub.3).sub.2O](VII), and a number in the range of from 1 to 100 of repeating units of formula (VIII):
[Si(CH.sub.3)(R.sup.16)O](VIII), wherein R.sup.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 randomly or in random alternating blocks, each block comprising two or more repeating units of formula (VII) or of formula (VIII) per block.

2. The composition according to claim 1, wherein each group Z1, Z2 and Z3 is independent of each other a group of the structure R.sup.i-{A[-C(R.sup.1)(R.sup.2)].sub.c[C(R.sup.3)(R.sup.4)].sub.d}.sub.e, and/or wherein at least one non-ionic compound is a compound of formula (II).

3. The composition according to claim 1, wherein in the ionic compound of formula (I), X is a monovalent cation not comprising a metal, selected from the group consisting of a proton and a group NR.sub.4.sup.+, wherein each R is independently selected from the group consisting of H, a branched C.sub.1-6-alkyl group, and an unbranched C.sub.1-4-alkyl group; one of Y1 and Y2 is an anionic polar group selected from the group consisting of COO.sup.?, SO.sub.3.sup.?, (O)SO.sub.3.sup.?, PO.sub.3.sup.2? and (O)PO.sub.3.sup.2?, and the other is hydrogen; and each group Z1, Z2 and Z3 is, independent of each other, a group of the structure R.sup.i-{A[C(R.sup.1)(R.sup.2)].sub.c[C(R.sup.3)(R.sup.4)].sub.d}.sub.e.

4. The composition according to claim 1, wherein in the compound of formula (I) X is selected from the group consisting of a proton and a group NR.sub.4.sup.+, wherein each R is independently selected from the group consisting of a H, a branched C.sub.1-6-alkyl group, and an unbranched C.sub.1-4-alkyl group, one of Y1 and Y2 is SO3.sup.?, and the other is hydrogen, each group Z1, Z2 and Z3 is, independent of each other, a group of the structure F.sub.3C(CF.sub.2).sub.a(CH.sub.2).sub.b{O[C(R.sup.1)(R.sup.2)].sub.c[C(R.sup.3)(R.sup.4)].sub.d}.sub.e, wherein: a is an integer in the range of from 0 to 2, and b is an integer in the range of from 1 to 6.

5. The composition of claim 1, further comprising water.

6. The composition of claim 1, wherein a mass ratio of the compound of formula (I) to the compound of formula (II) is in the range of from 1:4 to 1:1, and/or wherein a sum of the total amount of compound of formula (I) and the total amount of compound of formula (II) present in the composition is in the range of from 0.01 wt.-% to 0.5 wt.-%, based on the total weight of the composition.

7. The composition according to claim 1, wherein an equilibrium surface tension of the composition is less than 35 mN/m, as measured at 25? C. according to DIN 53914:1997-07 with a Kruess Tensiometer K 100 by the plate method, and/or wherein a pH of the composition is in a range of from 4.0 to 11.0.

8. A method of using the composition of claim 1, comprising: cleaning or rinsing a product by contacting the product with the composition, wherein the product comprises a substrate supporting a patterned material, the patterned material having line-space structures with a line width of 50 nm or below.

9. The method according to claim 8, wherein the cleaning or rinsing is part of a process of making integrated circuit devices, optical devices, micromachines, or mechanical precision devices, and/or wherein the substrate is a semiconductor substrate.

10. The method according to claim 8, wherein the composition is used for cleaning or rinsing so that a pattern collapse is prevented or reduced, a line edge roughness is reduced, watermark defects are prevented or removed, a photoresist-swelling is prevented or reduced, blob defects are prevented or reduced, and/or particles are removed.

11. The method according to claim 8, wherein: the patterned material is at least one selected from the group consisting of a patterned developed photoresist layer, a patterned barrier material layer, a patterned multi-stack material layer, and a patterned dielectric material layer; the patterned material has photoresist structures having an aspect ratio greater than 2 and/or patterned multi-stack line/space structures having an aspect ratio greater than 2; and/or the line-space structures have a line width of 32 nm or below.

12. A method of making a cleaned or rinsed product, the method comprising: preparing or providing a product comprising a substrate supporting a patterned material layer, the patterned material layer having line-space structures with a line width of 50 nm or below; preparing or providing a composition as defined in claim 1; and cleaning or rinsing the product with the composition to produce a cleaned or rinsed product.

13. The method according to claim 12, further comprising: providing a photoresist layer on a substrate, wherein the photoresist layer is an immersion photoresist layer, an EUV photoresist layer or an electron beam photoresist layer; exposing the photoresist layer to actinic radiation through a mask with or without an immersion liquid to produce an exposed photoresist layer; developing the exposed photoresist layer with a developer solution to obtain a pattern having line-space structures with a line width of 50 nm or below, thus producing the substrate supporting the patterned material layer; and optionally drying the cleaned or rinsed product.

Description

EXAMPLES

(1) The following examples are meant to further explain and illustrate the present invention without limiting its scope.

Example 1: Preparation of Test Compositions

(2) The following compositions I1, I1a and I2, according to the invention and compositions C1 and C2 as comparative compositions not according to the invention, (collectively referred to as the test compositions hereinafter) were prepared by conventional mixing of the components shown in table 1a. After mixing, the pH of the composition was adjusted by addition of a diluted aqueous ammonia solution, as required. In the compositions shown in tables 1a and 1b, the compound of formula (I) used therein is a compound of formula (I) wherein X is NH.sub.4.sup.+, Y1 is sulfonate, SO.sub.3, Y2 is hydrogen and the groups Z1, Z2 and Z3 have the same structure and are in each case a group of the formula F.sub.3CCF.sub.2CH.sub.2OCH.sub.2CH(C.sub.2H.sub.5).

(3) In the compositions shown in tables 1a and 1b, the compound of formula (II) is FTergent?212M (see above).

(4) In the compositions shown in table 1 b, the compound of formula (III) is Lutensol? T08, a C13 oxo alcohol ethoxylate detergent, commercially available from BASF SE.

(5) In the compositions shown in table 1b, the compound of formula (IV) is polyethylene glycol mono(tristyrylphenyl)ether (CAS? RN 99734-09-5).

(6) In the compositions shown in table 1 b, the compound of formula (V) is trimethylolpropane ethoxylate triacrylate, average M.sub.n=912 (CAS? RN 28961-43-5).

(7) In the compositions shown in tables 1a and 1 b, the compound of formula (VI) is KF351 A (see above).

(8) TABLE-US-00001 TABLE 1a Compositions according to the invention and comparative composition Composition Constituent I1 I1a I2 C1 C2 Compound of formula (I) 20-30 20-30 40-50 50 0 [mg] Compound of formula (II) 40-50 40-50 0 0 80 [mg] Compound of formula (VI) 0 0 60-70 0 0 [mg] Water [ml] 100 100 100 100 100 pH 9.6 11 10 10 9.6 Equilibrium surface tension 22 22 27 27 n.a. [mN/m] n.a.: no data point available

(9) The following compositions I1b, I2a, I3, I4 and I5 according to the invention and composition C3 as comparative composition not according to the invention, (also collectively referred to as the test compositions hereinafter) were prepared by conventional mixing of the components shown in table 1b. After mixing, the pH of the composition was adjusted by addition of a diluted aqueous ammonia solution, as required.

(10) TABLE-US-00002 TABLE 1b Compositions according to the invention and comparative composition Composition Constituent I1b I2a I3 I4 I5 C3 Compound 15-20 15-20 15-20 15-20 15-20 0 of formula (I) [mg] Compound 140-150 0 0 0 0 0 of formula (II) [mg] Compound 0 0 140-150 0 0 140-150 of formula (III) [mg] Compound 0 0 0 140-150 0 0 of formula (IV) [mg] Compound 0 0 0 0 140-150 0 of formula (V) [mg] Compound 0 140-150 0 0 0 0 of formula (VI) [mg] Choline 0 0 0 0 0 15-20 hydroxide [mg] Water [ml] 100 100 100 100 100 100 pH 9.6 9.6 9.6 9.6 9.6 10.4 Equilibrium 22 27 27 27 28 28 surface tension [mN/m]

Example 2: Determination of the Critical Micelle Concentration (CMVC)

(11) The CMVC was determined with a Kruess Tensiometer K 100 according to the plate method by measuring the equilibrium surface tension of a series of aqueous surfactant solutions having different concentrations. The resulting graph has usually two distinct regions. Below the CMVC, the equilibrium surface tension linearly depends in a wide range on the logarithm of the surfactant concentration. Above the CMVC, the equilibrium surface tension is more or less independent from the concentration of the surfactant. The data points of both regions can statistically be fitted by means of a simple linear regression. The CMVC is the intersection between the two linear regression lines fitted to the data in these regions.

Example 3: Equilibrium Surface Tension of the Compositions According to the Invention

(12) The equilibrium surface tension of aqueous surfactant solutions was determined at 25? C. according to DIN 53914:1997-07 with a Kruess Tensiometer K 100 by the plate method.

(13) The plate method uses a thin plate usually in the order of a few square centimeters in area. The plate is usually made from platinum having a high surface energy to ensure complete wetting. The force F on the plate due to wetting is measured via a tensiometer or microbalance and used to calculate the equilibrium surface tension using the Wilhelmy equation:

(14) $?=\frac{F}{I.Math.\cos \left(?\right)}$
where I is the wetted perimeter of the Wilhelmy plate and ? is the contact angle between the liquid phase and the plate. The results are shown in tables 1a and 1b above.

(15) From the results it can be seen that the compositions of the invention have equilibrium surface tensions of less than 30 mN/m and that preferred compositions of the invention have equilibrium surface tensions of less than 28 mN/m. The preferred composition I1 of the invention had an equilibrium surface tension of less than 25 mN/m.

Example 4: Storage Stability of the Compositions of the Invention

(16) Test compositions were prepared as explained in example 1 above and stored for 9 weeks at 25? C. and 40% relative humidity. Before (i.e. directly after preparation of the compositions) and after this storage period, the test compositions were in each case analyzed for their CMC curves by means of surface tension measurement as described in example 2 above: the equilibrium surface tension was in each case measured for a series (i.e. more than ten) of aqueous surfactant solutions having different concentrations up to a 100-fold dilution (with deionized water). The results from this test are shown in table 2 below.

(17) TABLE-US-00003 TABLE 2 Storage stability of compositions Equilibrium surface tension (up to Composition 100-fold dilution, at CMC) I1 I1a I2 Equilibrium surface tension directly 38 38 41 after preparation [mN/m]: Equilibrium surface tension after 9 38 46 55 weeks storage period [mN/m]:

(18) From the results of this example 4 it can be seen that composition I1 according to the invention showed the best storage stability under the storage conditions because its equilibrium surface tension did not change (increase) over the storage period. It could also be seen from the results of this experiment that the most suitable pH of the compositions of the present inventionfor the purposes of optimized storage stabilityis below pH 10, preferably at or below pH 9.6: for compositions of the invention with a pH at or below 9.6 an extremely low or no degradation of surfactants contained therein was found.

Example 5: Rinse Performance of the Compositions of the Invention and of Comparative Compositions by Measurement of Critical Dimension

(19) Si semiconductor test wafers were coated with a standard positive photoresist, followed by a standard sequence of process steps: baking of the photoresist, exposing to actinic radiation, developing the positive resist with an aqueous developer solution (containing 2.38 wt.-% TMAH) to create line-space/via-hole structures with a line width/via-hole diameter of 40 nm/70 nm on the wafer's surface, as is generally known in the art.

(20) Line-space structures on the test wafers so created were then rinsed with compositions according to the invention I1, I1a, I1b, I2, I2a, I3, I4 and I5 and with comparative compositions C1, C2 and C3 (all compositions as defined in example 1 above, all experiments performed on separate semiconductor wafers per test composition) after the step of developing, without drying the liquid puddle on the wafer, followed by spraying each test composition (as rinse solutions) for 5 seconds at a flow rate of 10 ml/sec onto the test wafers' surfaces. For further comparison, said line-space structures were also rinsed under the same conditions (after the step of developing) with a standard aqueous defect reduction rinse solution of the prior art comprising an anionic, unbranched (linear) fluoroalkyl compound as single surfactant and which had a pH in the range of from 9.4 to 9.7 and a surface tension in the range of from 25 to 30 mN/m (referred to as composition POR hereinafter).

(21) Subsequent to the rinses with the compositions defined here above, the Critical Dimensions (CD) line width/via diameters were measured by averaging 30 respective measured values in each case after the rinse by a by a critical dimension scanning electron microscope (CD SEM; KLA 8100XP by KLA Tencor, USA) in dense areas (i.e. repeating the pattern placement in both X and Y dimension), semi-dense areas (i.e. repeating the pattern placement in only X or Y dimension) and iso areas (i.e. every individual pattern was isolated from each other), and defined as the Critical Dimensions relevant for this experiment. The Critical Dimensions generally describes the size of the patterns present on a semiconductor wafer such as line/space width or diameters for the via/hole, more specifically, the smallest size shown on the semiconductor wafer.

(22) The Critical Dimensions measured by the method as explained above after rinses with the compositions according to the invention I1, I1a, I1b, I2, I2a, I3, I4 and I5 with comparative compositions C1, C2 and C3 and with the composition POR were collected and compared by the CD software of the scanning electron microscope. Then, the Critical Dimension differences between the compositions according to the invention I1, I1a, I1b, I2, I3, I4 and I5 and comparative compositions C1, C2 and C3 on the one hand and the composition POR on the other hand were calculated by the software and presented in the format of maximum Critical Dimension proximity bias to composition POR (i.e. the maximum CD deviation between the wafer rinsed with a test composition and the wafer rinsed with the standard rinse solution composition POR) in the area of interest (dense, semi-dense or iso, as shown in tables 3a and 3b below). Maximum Critical Dimension proximity bias values equal to or below 2 nm in relation to the respective Critical Dimension values measured with standard composition POR indicate preferred rinsing results achieved with the test compositions. The values for Maximum Critical Dimension proximity bias should be as low as possible and a value of 2 nm thereof is a preferred upper threshold which is acceptable for further processing where the performance of the final device or product will not be limited due to e.g. a poor cleaning or rinsing result. The results from this test are shown in tables 3a and 3b below.

(23) TABLE-US-00004 TABLE 3a Measurement of Critical Dimensions-Part A Composition Critical Dimension I1 I1a I2 C1 C2 Maximum CD proximity bias 1.8 2.5 1.6 3.5 1.4 to composition POR in dense area (width change of the pattern in nm) Maximum CD proximity bias 1.9 3 1.4 3.2 3.0 to composition POR in semi- dense area (width change of the pattern in nm) Maximum CD proximity bias 0.7 1.9 2.1 2.8 3.4 to composition POR in iso area (width change of the pattern in nm)

(24) TABLE-US-00005 TABLE 3b Measurement of Critical Dimensions-Part B Composition Critical Dimension I1b I2a I3 I4 I5 C3 Maximum CD proximi- 1.4 1.7 2.0 2.0 1.8 6.5 ty bias to composition POR in semi-dense area (width change of the pattern in nm)

(25) From the results of this example 5 it can be concluded that a composition according to the invention (comprising as primary surfactant an ionic compound of formula (I) and as secondary surfactant at least one non-ionic compound comprising one or more polyalkyloxy and/or polyalkylenoxy groups, i.e. composition I1, I1a, I1b, I2, I2a, I3, I4 or I5) shows better rinse results (probably due to a higher potential for defect reduction) than a comparative composition comprising only an ionic compound of formula (I) (i.e. comparative composition C1) or a comparative composition comprising only a non-ionic compound comprising one or more polyalkyloxy and/or polyalkylenoxy groups (i.e. comparative composition C2), thus illustrating a synergetic effect of the compositions of the invention comprising both a primary surfactant and a secondary surfactant, as defined herein. The least favourable results in this test model were obtained with comparative test composition C3 comprising choline hydroxide as first surfactant and as a second surfactant a compound of formula III. The comparative test composition C3 clearly failed to meet the success criteria of the present test model (Maximum Critical Dimension proximity bias values equal to or below 2 nm in relation to the respective Critical Dimension values measured with standard composition POR) and is therefore not regarded as suitable for cleaning or rinsing a product comprising a substrate and supported thereon a patterned material layer having line-space structures with a line width of 50 nm or below.

(26) Best results were achieved with the composition I1 according to the invention, showing the best rinsing results in the test setting.

Example 6: Liquid Particle (Micelle) Content of the Compositions

(27) Compositions I1 (according to the invention) and C1 (comparative composition) were prepared as explained in example 1 above. Both compositions were filtrated through a HDPE (high density poly ethylene) filter (0.02 ?m pore size, Entegris) for 24 hrs. After filtration, liquid particle content of both compositions was determined by light scattering using a Rion KL 27 particle counter (Rion Co., Ltd. JP), for the method see e.g. K. Kondo et al. Measurement of Particles in Liquid Materials Using the Light Scattering Method, The proceeding of Interfacial Nano Electrochemistry, March 2013.

(28) Generally, light scattering occurs when a sample introduced through the nozzle of a particle counter instrument is irradiated with light and then the particles pass through the light. The scattered light is detected by the photo detector and is converted into electrical signals which can be analyzed: the size of the electrical signals represents the particle size and the frequency of scattered-light detection represents the particle count (number of particles).

(29) The data was sampled in each case by averaging three single measurement values per test composition. The results of this experiment are shown in table 4 below.

(30) TABLE-US-00006 TABLE 4 Liquid particle count in the test compositions Particle I1 C1 size [?m] [particles/ml] [particles/ml] 0.02 155 Exceeding measuring range 0.05 84 Exceeding measuring range 0.1 37 Exceeding measuring range 0.2 8 Exceeding measuring range 0.5 1 Exceeding measuring range

(31) The term Exceeding measuring range in table 4 means that the number of particles detected by the particle counter instrument was too high to be counted in the experimental setting.

(32) From the data shown in table 4 above it can be seen that a composition according to the invention contains significantly less particles than a comparative composition not according to the invention. These particles mainly comprise partially soluble surfactant aggregates (micelles) which can pass through the pore of filter upon squeezing. Therefore, solid (hard) particles were filtered but surfactant aggregates were not (or to a much lesser extent) filtered in this experiment. However, the particles not filtered (surfactant aggregates) can have a negative impact on the cleaning or rinsing effect of a respective composition.

Example 7: Equilibrium Contact Angle of the Compositions of the Invention on a Product Comprising a Substrate

(33) A composition according to the invention, composition 1 b (similar to composition I1 of example 1, but with a lower collective concentration of compound of formula (I) and compound of formula (II) of 0.05 wt.-% relative to the total mass of the composition) and a comparative composition C1 (not according to the invention) were prepared as explained in example 1 above.

(34) A flat semiconductor wafer coated with a common unexposed positive photoresist (substrate) was placed on the horizontal support of a Kr?ss drop shape analyzer (type DSA 100, Kr?ss GmbH, Germany), fitted with an optical screen during usage. For adding the test compositions, a microliter syringe was positioned at the center of the substrate and connected to the micromanipulator of the drop shape analyzer. The micromanipulator is used to adjust the position of the needle tip of the syringe carefully above the wafer. The tip of the syringe was positioned a few micrometers away from the surface of the substrate to eliminate impact effect when a droplet of a test composition is released. The droplet volume was selected in each case to be 2 ?l so that gravity effects were negligible. The drop was recorded and applied on the substrate with the defined volume by exact movement of the syringe of the contact angle meter using a charge-coupled device (CCD) camera, and equilibrium contact angles were measured directly (0 seconds) after the test composition had been applied onto the substrate's surface and again 10 seconds thereafter. The results from this experiment are shown in table 5 below.

(35) TABLE-US-00007 TABLE 5 Equilibrium contact angles of compositions Contact angle directly (0 s) Contact angle 10 s after application onto after application Composition substrate onto substrate I1b 23? 17.3? C1 42? 41.3?

(36) From the above results in table 5 it can be seen that the equilibrium contact angle of a composition according to the invention is much smaller than the contact angle of a comparative composition not according to the invention, showing that the composition according to the invention has a better wettability (i.e. can better wet) the substrate's surface (i.e. the photoresist-coated surface of a semiconductor wafer) than a comparative composition not according to the invention. Compositions which show a good wettability of a substrate usually achieve better cleaning or rinsing results on said substrate and/or better defect reduction results than compositions which show a poorer wettability of said substrate.

Example 8: Rinse Performance of the Compositions of the Invention and of Comparative Compositions Under the Aspect of Pattern Collapse

(37) Si semiconductor test wafers were coated with a standard positive photoresist, followed by a standard sequence of process steps: baking of the photoresist, exposing to actinic radiation, developing the positive resist with an aqueous developer solution (containing 2.38 wt.-% TMAH) to create line-space/via-hole structures with a line width/via-hole diameter of 40 nm/70 nm on the wafer's surface, as is generally known in the art.

(38) Line-space structures on the test wafers so created were then rinsed with compositions according to the invention I1b, I2a, I3, I4 and I5 and with comparative composition C3 (all compositions as defined in example 1 above, all experiments performed on separate semiconductor wafers per test composition) after the step of developing, without drying the liquid puddle on the wafer, followed by spraying each test composition (as rinse solutions) for 5 seconds at a flow rate of 10 ml/sec onto the test wafers' surfaces.

(39) Subsequent to the rinses with the compositions defined here above, the test wafers were coated with a thin protective layer of platinum (as is known in the art, to enhance surface conductivity, thickness of the platinum layer about <0.5 nm). Then, 5 test areas of 10 ?m.sup.2 each were randomly selected per test wafer and inspected for the number of pattern collapses of the line-space/via-hole structures previously created (see above) per test area by top down (or slightly tilted) view scanning electron microscopy (SEM) with a Hitachi SU 8220 scanning electron microscope. The numbers of collapsed patterns from the 5 test areas on a test wafer were counted and an average of the numbers obtained was rounded off and recorded as a result (per test wafer).

(40) The results of this experiment are shown in table 6 below.

(41) TABLE-US-00008 TABLE 6 Inspection for pattern collapses of line-space structures after rinses with the test compositions Composition Critical Dimension I1b I2a I3 I4 I5 C3 Average number of 0 5 2 6 10 15 pattern collapses of line-space structures in 10 ?m.sup.2 test areas after rinses with the test compositions

(42) From the results of this example 8 as shown above in table 6 it can be seen that the compositions according to the invention, comprising as primary surfactant an ionic compound of formula (I) and as secondary surfactant at least one non-ionic compound comprising one or more polyalkyloxy and/or polyalkylenoxy groups (i.e. composition I1b, I2a, I3, I4 or I5), all show significantly better rinse results on a patterned material layer having line-space structures with a line width of 50 nm or below than a comparative composition (i.e. comparative composition C3) comprising an ionic compound not according to the invention (i.e. choline hydroxide) and as secondary surfactant at least one non-ionic compound comprising one or more polyalkyloxy and/or polyalkylenoxy groups, i.e. rinses with said compositions according to the invention resulted in a significantly lower number of pattern collapses of the rinsed structures than a rinse with said comparative composition.

(43) The compositions I1b, I2a, I3, I4 according to the invention showed particularly good rinse results on a patterned material layer having line-space structures with a line width of 50 nm or below in this test method, with a particularly low number of pattern collapses of the rinsed structures. The compositions I1b, I2a, I3, I4 therefore represent preferred compositions according to the present invention.

(44) The composition I1b according to the invention showed the best rinse results on a patterned material layer having line-space structures with a line width of 50 nm or below in this test method, with no pattern collapses of the rinsed structures at all. The composition I1b therefore represents a particularly preferred composition according to the present invention.