Use of metal-containing and / or metalloid keto acid oxime salts and / or keto acid oxime salts of metal-containing compounds as patterning agents

Abstract

The invention relates to the use of keto acid oxime salts of metal-containing and / or metalloid-containing keto acid oxime salts and / or keto acid oxime salts of metal-containing compounds as functional metal-containing and / or metalloid-containing keto acid oxime salts for use as patterning agents in EUV and electron beam lithography, application in the field of semiconductor chip production and in the field of mask production, sensors and direct patterning of functional materials for photonics or catalysis. Preferably, a keto acid oxime salt of a metal-containing or metal compound has one of the following structural forms: Formula (I) or Formula (II) wherein: R1 and R2 represent hydrogen (H), an organic compound such as aliphatic C1 to C10, aromatic, cyclic, polymerizable organic compound such as acrylate, methacrylate, vinyl, etc., or a combination of these; m represents a central metal or metalloid atom linked to a keto acid oxime group, and / or a central metal atom linked to another group such as an oxide, a hydroxide or the like, or a central metal atom linked to another group R3, and the other group R3 is a carboxylic acid ester (such as an acetate or the like), a glycine ester, a xanthate, an alkyl group, an aryl group or the like. # imgabs0 #

Description

[0001] The present invention relates to the use of specific compounds as patterning agents in photolithography and / or electron beam patterning. It can be used in the following fields: semiconductor chip production (especially but not limited to EUV wavelengths) and direct patterning of functional materials for applications such as masks, sensors, photonics or catalysis in the semiconductor industry.

[0002] Photolithography has been the basis for manufacturing devices in the micron and nanometer range in the semiconductor industry. It uses a resist (usually a photosensitive polymer material) to perform imaging, and transfers the pattern to the substrate via a process of plasma etching or by stripping after metal (oxide) deposition. Currently, the pursuit of ever-shrinking critical dimensions from microns to tens of nanometers has been made possible by the use of increasingly shorter wavelength imaging radiation (193 nm since the early 2000s) combined with some technological ingenuity in the past decade (such as immersion lithography and multiple exposure patterning). The realization of higher resolution by simpler direct light exposure occurs at a large increase in capital cost, because it requires shorter wavelength imaging radiation and suitable resists to achieve its advantages.

[0003] In recent years, EUV technology (13.5nm wavelength) has become a powerful alternative to ArF immersion lithography for high-volume manufacturing. In order to take advantage of the EUV light source (which has the disadvantage of limited power), it is necessary to develop new resist materials that have high sensitivity at this wavelength, enable high resolution, exhibit low line edge roughness (LER), and at the same time maintain pattern fidelity and uniformity. Chemically amplified resists (CARs), which are mainly organic, perform very well in 248nm and 193nm lithography, but are very transparent in EUV wavelengths.

[0004] This presents a major problem as it causes a reduction in the sensitivity of these resists. On the other hand, incorporation of certain metals in thin resists causes high EUV absorbance (causing improved sensitivity), mitigation of photon shot noise effects, and simultaneously acts as a durable etch mask.

[0005] For these reasons, new resists containing atoms that show increased absorbance at EUV wavelengths have been proposed as alternatives to CAR.

[0006] Fig.13 The graph in provides theoretically calculated EUV absorption cross sections for various elements. The data here provide guidance for the selection of elements in EUV resists that will increase radiation absorption. Generally, elements with higher EUV absorption cross sections are preferred.

[0007] It is therefore an object of the present invention to provide patterning agents (e.g. photoresists) which have high EUV absorbance (leading to improved sensitivity), high patterning resolution and low line edge roughness and at the same time serve as durable etch masks in semiconductor chip production. It would be desirable if the same patterning agent could also be used as an electron beam sensitive resist in electron beam lithography for direct patterning of functional materials (e.g. high refractive index nanopatterns for photonic applications or high absorbance materials for EUV photomasks).

[0008] According to the present invention, this object is achieved by the use of oxime salts of ketoacids containing metals and / or metalloids and / or oxime salts of ketoacids containing metal compounds, which are used as patterning agents in photolithography and electron beam lithography, and are applied in the field of semiconductor chip production and in the field of direct patterning of functional materials for mask production, sensors, photonics or catalysis.

[0009] Unexpectedly, metal- and / or metalloid-containing ketoacid oxime salts and / or ketoacid oxime salts containing metal compounds exhibit exactly the desired properties in terms of high EUV absorbance or electron beam sensitivity (resulting in the desired sensitivity).

[0010] In particular, EUV lithography uses shorter wavelength radiation that requires the development of new photoresists that are sensitive to shorter wavelengths (13.5 nm). Since conventional carbon-based resists are fairly transparent at this wavelength, new resists containing heavier elements that highly absorb EUV radiation are needed. It is logical to incorporate metals (such as tin) with high absorption cross-sections at EUV wavelengths in the resist to improve its sensitivity ( Figure 1 ). However, exposure of the resist occurs via secondary electrons generated in the resist volume during EUV exposure. The degree of effectiveness of these electrons in breaking bonds in the resist is also important. Therefore, in the present invention, instead of focusing on metals containing high EUV absorption cross-sections, empirical means are used to consider the efficacy of secondary electrons in the exposure of the resist. For example, nickel and zinc have similar EUV absorption cross-sections. However, a currently preferred resist containing zinc requires a much lower exposure dose than a nickel resist with the same ligand environment, indicating that interactions between secondary electrons play a major role during the irradiation process.

[0011] Typically, the oxime salt of a keto acid containing a divalent metal or metalloid or metal compound may have one of the following structural forms:

[0012]

[0013] in:

[0014] R1 and R2 represent hydrogen (H), an organic group such as an aliphatic C1 to C 10, aromatic, cyclic, polymerizable organic groups such as acrylate, methacrylate, vinyl, etc., or combinations of these; and

[0015] M represents a central metal or metalloid atom which may be monovalent, divalent, trivalent, tetravalent, pentavalent or higher valent and which is connected to the ketoic acid oxime group in a monodentate, bidentate or tridentate manner, and / or represents a central metal atom connected to other groups such as oxides, hydroxides, etc., or M represents a central metal atom connected to another group R3, and the other group R3 is a carboxylate (such as acetate, etc.), glycine ester, xanthate, alkyl, aryl, etc.

[0016] Preferably, the metal atom is selected from the group consisting of zinc, indium, aluminum, nickel, magnesium and tin.

[0017] Further preferred embodiments of the invention are listed in dependent claims 2 to 15 .

[0018] Preferred embodiments of the present invention are described in more detail hereinafter with reference to the accompanying drawings depicted below:

[0019] Figure 1 Dose-to-gel curves of zinc(II) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam; (c) sensitivity values ​​of the resist obtained with various developers;

[0020] Figure 2 (a) Half-pitch 22 nm (325 mJ / cm) using zinc (II) methoxyiminopropionate resist 2 )、(b) half-pitch 18nm (297mJ / cm 2 ) and (c) half-pitch 16nm (290mJ / cm 2 )EUV lithography of lines;

[0021] Figure 3 Electron beam lithography of 5 nm wide lines patterned using zinc(II) methoxyiminopropionate resist;

[0022] Figure 4 Dose-gel curves of hydroxyiminopropionate indium(III) resist exposed to (a) EUV and (b) electron beam; (c) sensitivity values ​​of the resist obtained with various developers;

[0023] Figure 5 (a) Half-pitch 22 nm (222 mJ / cm) using hydroxyiminopropionic acid indium (III) resist 2 )、(b) half-pitch 18nm (223mJ / cm 2 ) and (c) half-pitch 16nm (199mJ / cm2 )EUV lithography of lines;

[0024] Figure 6 Dose-gel curves of indium(III) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam; (c) sensitivity values ​​of the resist obtained with various developers;

[0025] Figure 7 (a) Half-pitch 22nm (193mJ / cm) using indium(III) methoxyiminopropionate resist 2 )、(b) half-pitch 18nm (194mJ / cm 2 ) and (c) half-pitch 16nm (173mJ / cm 2 )EUV lithography of lines;

[0026] Figure 8 Dose-gel curves of aluminum(III) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam; (c) sensitivity values ​​of the resist obtained with various developers;

[0027] Fig. 9 (a) Half-pitch 50 nm (64 mJ / cm) using methoxyiminopropionic acid aluminum (III) resist 2 ) and (b) half-pitch 35nm (51mJ / cm 2 )’s EUV lithography;

[0028] Fig.10 Dose-gel curves of nickel(II) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam; (c) sensitivity values ​​of the resist obtained with various developers;

[0029] Fig.11 Dose-gel curves of magnesium(II) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam; (c) sensitivity values ​​of the resist obtained with various developers;

[0030] Fig.12 Dose-gel curves of methoxyiminopropionate tin(II) resist exposed to (a) EUV and (b) electron beam; (c) sensitivity values ​​of the resist obtained with various developers;

[0031] Fig.13 Atomic absorption cross section σ of elements with atomic number Z from 1 to 86 under EUV (λ=13.5 nm) a ;

[0032] Fig.14 EUVL dose-gel curve of Zn(MIP)2.2H2O resist;

[0033] Fig.15 EUV patterning results of Zn(MIP)2.2H2O resist without an underlayer.

[0034] Fig.16 EUV patterning results of Zn(MIP)2 (anhydrous) without an underlying layer.

[0035] Fig.17 EUV patterning results of Zn(MIP)2 (anhydrous) in the case of underlying layer SHT101;

[0036] Fig.18 EUV patterning results of Zn(MIP)2 (anhydrous) with underlying layer SHT101 and post-exposure bake at 80°C and 60 seconds;

[0037] Fig.19 EUV patterning results of Zn(MIP)2 (anhydrous) with underlying layer PRE102 and post-exposure bake at 90°C and 60 seconds;

[0038] Fig. 20 EUV patterning results of Zn(MIP)2.2H2O resist without an underlayer and with developer anisole; and

[0039] Fig.21 EUV patterning results of Zn(MIP)2 (anhydrous) without an underlayer and using anisole as developer.

[0040] In the following, various methods for making metal and metalloid compounds for photolithographic patterning of substrates (e.g., extreme ultraviolet (EUV) and electron beam lithography) are described in more detail. In general, the family of compounds of keto acid oxime salts can be used for these applications in terms of photoresists, electron beam resists, precursors for metal or metal oxide patterning.

[0041] Since metal / metalloid keto acid oxime salts are known in the art, one would expect them to be commercially available, but they are not currently. Therefore, they must be synthesized in the laboratory. The first step involves the condensation of an α-keto acid with an amine to give an α-oxime acid.

[0042]

[0043] The α-oxime acid is then reacted with a metal / metalloid salt (eg nitrate or chloride) in the presence of a suitable base to give the metal / metalloid keto acid oxime salt as shown below. The reaction can be carried out in an organic medium or an aqueous medium.

[0044]

[0045] The synthesized metal / metalloid ketoic acid oxime salts were found to be sensitive to high energy electrons (0.5 kV to 300 kV), extreme ultraviolet (EUV) radiation (92 eV, 13.5 nm), and other types of high energy radiation below 250 nm wavelength. Such sensitivity to electrons and EUV radiation (among others) makes them patternable, and they will be referred to hereafter as "metal (metalloid) containing patterning agents" or simply "patterning agents".

[0046] Since the condensation involves an α-keto acid and an amine to give an α-oxime acid, the organic group (R1) attached to the amine and the organic group (R2) attached to the α-keto acid can be modified separately and independently. These groups can be hydrogen (H), aliphatic (C1-C 10 ), aromatic, cyclic, polymerizable groups (acrylate, methacrylate, vinyl, etc.), or combinations of these. First, we provide representative examples of modifications that present an organic group (R1, light gray) attached to an amine while keeping the group in R2 (dark gray) as H.

[0047]

[0048] Next, some representative examples of modifications of the organic group (R2) attached to the α-keto acid that keep the group in R1 fixed are provided.

[0049]

[0050] Additional flexibility can also be obtained by adding halogen groups to the α-keto acids. A representative example for pyruvic acid is given below.

[0051]

[0052] From the above representative examples, one can see that there are at least 20 possible ways in which the organic environment around the central metal atom can be modified. Such versatility in the synthesis of α-oxime acids and their ultimate metal or metalloid salts therefrom provides the customizability of the sensitivity of the patterning agent to high-energy electrons and photons (for example, in terms of photoresists), solubility in organic solvents, and film-forming properties on silicon substrates. At least 40 patterning agent resists of different metals and metalloids were synthesized using the above process, 30% of which were spin-coated and could be patterned using electrons and photons. The following are representative examples of resists prepared by the above synthesis process that were found to be patternable.

[0053]

[0054]

[0055] Although the above representative examples show a central metal atom connected to a keto acid oxime group, it may also have a central atom connected to other groups (e.g., oxides, hydroxides) or any group R3 (e.g., carboxylates (acetates, etc.), glycine esters, xanthates, alkyl groups, aryls, etc.). The central metal atom may be monovalent, divalent, or higher valent.

[0056]

[0057] Adducts with a Lewis base bonded to the central metal atom are also possible.

[0058] The present invention also provides a method for patterning a semiconductor surface by coating a surface with a patterning agent and irradiating the coated surface with a predetermined photon irradiation pattern or an electron beam pattern. In the method, an appropriate amount of patterning agent (herein, a photoresist) is dissolved in a solvent (e.g., 2-methoxyethanol) to obtain a concentration of 0.0125 gm / ml to 0.1 gm / ml. For a film thickness less than 50 nm, it is found that a concentration in the range of 0.0125 gm / ml to 0.025 gm / ml is suitable. These dissolved resists are spin-coated on a pre-cleaned semiconductor substrate (e.g., a silicon substrate) with a suitable rotational speed (e.g., a rotational speed of 1800 rpm). They are then exposed to photon radiation (e.g., EUV radiation) or exposed to electrons (e.g., 100 kV electrons) in an electron beam recorder through a mask at a photon source. Photon radiation can be generated, for example, in a synchrotron, such as at the Swiss Light Source (SLS) in PSI in Villigen, Switzerland (for more details on SLS visit www.psi.ch).

[0059] In order to study the sensitivity of resist to draw dose-gel curve, use EUV or electronics to expose them with various doses.These resists are developed with various organic solvents (such as methanol, ethanol, isopropanol, 2-methoxyethanol, 1-methoxy-2-propanol, 1-butoxyethanol, 3-methoxy-1-butanol, 2-methoxyethyl acetate and 1-methoxy-2-propyl acetate).Use the same solvent that makes them develop to rinse them.For dose-gel curve, 10 seconds development, followed by 5 seconds of rinsing, then use nitrogen to dry up.After exposure, resist shows negative behavior.

[0060] For EUV patterning, the resist is exposed through a grating mask. On the other hand, a predetermined pattern is used for electron beam lithography.

[0061] Figure 1Shown are the dose-gel curves of zinc(II) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam. Figure 1 (c) shows the sensitivity values ​​of the resist obtained with various developers.

[0062] Figure 2 (a) Half-pitch 22 nm (325 mJ / cm 2 )、(b) half-pitch 18nm (297mJ / cm 2 ) and (c) half-pitch 16nm (290mJ / cm 2 ) lines of EUV lithography.

[0063] Figure 3 Electron beam lithography of 5 nm wide lines patterned using zinc(II) methoxyiminopropionate resist is shown.

[0064] Figure 4 Now shown are the dose-gel curves of hydroxyiminopropionate indium(III) resist exposed to (a) EUV and (b) electron beam. Figure 4 (c) shows the sensitivity values ​​of the resist obtained with various developers. Figure 5 (a) Half-pitch 22 nm (222 mJ / cm) using hydroxyiminopropionic acid indium (III) resist 2 )、(b) half-pitch 18nm (223mJ / cm 2 ) and (c) half-pitch 16nm (199mJ / cm 2 ) lines in EUV lithography. Due to under-dosage, the features here are slightly smaller than half the designed pitch.

[0065] Figure 6 Shown are the dose-gel curves of indium(III) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam. Figure 6 (c) shows the sensitivity values ​​of the resist obtained with various developers. '*' indicates data from poor development characteristics. 'N / A' indicates that data could not be acquired due to excessive scum on the surface. Figure 7 (a) Half-pitch 22 nm (193 mJ / cm) using indium(III) methoxyiminopropionate resist 2 )、(b) half-pitch 18nm (194mJ / cm 2 ) and (c) half-pitch 16nm (173mJ / cm 2 ) lines in EUV lithography. Due to under-dosage, the features here are slightly smaller than half the designed pitch.

[0066] Figure 8Shown are the dose-gel curves of aluminum(III) methoxyiminopropionate resist exposed to (a) EUV and (b) electron beam. Figure 8 (c) shows the sensitivity values ​​of the resist obtained with various developers: MeOH = methanol; 1M2P = 1-methoxy-2-propanol; 3M1B = 3-methoxy-1-butanol; 2-MEA = 2-methoxyethyl acetate. Fig. 9 (a) Half-pitch 50 nm (64 mJ / cm) using methoxyiminopropionic acid aluminum (III) resist 2 ) and (b) half-pitch 35nm (51mJ / cm 2 ) at smaller pitches, the resist exhibits excessive scumming between the lines.

[0067] Fig.10 Shown are the dose-gel curves of methoxyiminopropionate nickel(II) resist exposed to (a) EUV and (b) electron beam. Fig.10 (c) shows the sensitivity values ​​of the resist obtained with various developers. 'N / A' means that data could not be acquired because no features were seen on the surface.

[0068] Fig.11 Shown are the dose-gel curves of magnesium(II) methoxyiminopropionate resist exposed to (a) EUV and (b) e-beam. Fig.11 (c) shows the sensitivity values ​​of the resist obtained with various developers. 'N / A' means that no data could be acquired due to no development at all.

[0069] Fig.12 Shown are the dose-gel curves of methoxyiminopropionate tin(II) resist exposed to (a) EUV and (b) electron beam. Fig.12 (c) shows the sensitivity values ​​of the resist obtained with various developers. '*' indicates data from poor development characteristics. 'N / A' indicates that data could not be acquired due to excessive scum on the surface.

[0070] The main advantages of metal / metal compound ketoacid oxime salt resist systems include

[0071] ■ Featuring new molecular resist systems with low molecular mass (<500 Daltons), which becomes critical for sub-10 nm patterning.

[0072] ■ While maintaining a mass of nearly 500 Daltons, the organic environment around the central metal (metalloid) atom can be tailored (in at least 15 possible ways).

[0073] ■ Compatible with both EUV and e-beam lithography.

[0074] ■ Incorporates a general protocol for patterning metal / metalloid containing functional resists.

[0075] ■ Possibility to incorporate metal atoms (eg aluminum) that do not pose a risk of contamination in semiconductor fabrication plants.

[0076] ■ Possibility of doping with heavy elements (eg cesium) to further improve EUV or electron beam absorption to increase sensitivity.

[0077] ■High sensitivity to EUV and electron beam exposure.

[0078] ■Resists are capable of sub-5nm lithography, and angstrom-level lithography is also possible using electron beams.

[0079] Fig.13 Theoretically calculated EUV absorption cross sections for various elements are provided. The data here provide guidance for the selection of elements in EUV resists. Generally, elements with higher EUV absorption cross sections are preferred. In detail, Fig.13 The atomic absorption cross sections σ of elements with atomic numbers Z from 1 to 86 under EUV (λ=13.5 nm) are shown. a .

[0080] Fig.14 The EUVL dose-gel curve of Zn(MIP)2.2H2O resist is shown. In the following, EUV patterning results with Zn(MIP)2.2H2O resist or Zn(MIP)2 (anhydrous) resist are presented.

[0081] Fig.15 The EUV patterning results of Zn(MIP)2.2H2O resist without an underlying layer are shown.

[0082] Fig.16 Depicted are EUV patterning results of Zn(MIP)2 (anhydrous) also without an underlying layer.

[0083] Fig.17 The EUV patterning results of Zn(MIP)2 (anhydrous) in the case of the underlying layer SHT101 are shown. Fig.18 EUV patterning results of Zn(MIP)2 (anhydrous) with an underlying layer of SHT101 and a post-exposure bake at 80°C and 60 seconds are presented.

[0084] Fig.19 EUV patterning results of Zn(MIP)2 (anhydrous) with different underlying layers PRE102 and post-exposure baking at 90°C and 60 seconds are shown.

[0085] Fig. 20depicts the EUV patterning results of Zn(MIP)2.2H2O resist without an underlying layer and now with a different developer, anisole, Fig.21 The EUV patterning results of Zn(MIP)2 (anhydrous) without an underlayer and using anisole as the developer are shown.

Claims

1. Use of ketoximate salts of metals and / or metalloids and / or ketoximate salts of metal compounds, wherein the ketoximate salts are used as patterning agents in EUV and electron beam lithography, and are applied in the field of semiconductor chip production and in the field of direct patterning of functional materials for mask production, sensors, photonics or catalysis.

2. The method according to claim 1, wherein the central metal or metalloid atom connected to the ketoacid oxime group is monovalent, divalent, trivalent, tetravalent, pentavalent or higher.

3. The use according to claim 1 or 2, wherein the composition of the keto acid oxime salt containing a divalent metal or metalloid compound has one of the following structural forms: in: R1 and R2 represent hydrogen (H), an organic group such as an aliphatic C1 to C 10 , aromatic, cyclic, polymerizable moieties such as acrylate, methacrylate, vinyl, epoxy, oxetane, etc., or combinations of these; and M represents a central metal or metalloid atom with characteristic valence as claimed in claim 2 which is connected to the ketoic acid oxime group in a monodentate, bidentate or tridentate manner, and / or M represents a central metal or metalloid atom connected to other groups such as oxides, hydroxides, water, etc., or a central metal or metalloid atom connected to another group R3, and the other group R3 is a carboxylate such as acetate, glycine ester, xanthate, alkyl, aryl, or a polymerizable part such as acrylate, methacrylate, vinyl, epoxy, oxetane, etc., or a combination of these.

4. Use according to any one of the preceding claims, wherein the metal is selected from the group comprising zinc, indium, aluminum, nickel, magnesium and tin.

5. Use according to any one of the preceding claims, wherein the metal content is up to 40% by weight of the total weight of the chemical composition.

6. Use according to any one of the preceding claims, wherein the metal content is up to 6 atomic % of the chemical composition.

7. The use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing keto-acid oxime salt and / or the keto-acid oxime salt of a metal compound is suitable for producing a coating formulation by dissolving it in an organic solvent, the coating formulation being a formulation cast on a substrate or on an underlying coating on a substrate, and wherein the coating can be patterned by direct irradiation or using a mask.

8. The use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing ketoic acid oxime salt and / or the metal-containing ketoic acid oxime salt is used to form a resist film by applying a patterning agent to a semiconductor substrate and baking the composition at about 50° C. to about 150° C. for 0.1 minute to about 20 minutes.

9. Use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing ketoacid oxime salts and / or ketoacid oxime salts containing metal compounds are patterned using electron beam or EUV lithography with or without a photoinitiator or photoacid generator (PAG).

10. Use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing ketoic acid oxime salt and / or the ketoic acid oxime salt of the metal compound is such that the patterning agent-coated substrate is irradiated with radiation of light at a wavelength of 13.5 nm.

11. The use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing ketoic acid oxime salt and / or the ketoic acid oxime salt of the metal compound is such that the patterning agent-coated substrate is irradiated with electrons at 0.5 kV to 300 kV.

12. The use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing ketoic acid oxime salt and / or the ketoic acid oxime salt of a metal compound allows the coated substrate to be irradiated along a selected pattern to form an irradiated structure having areas of irradiated coating and areas of unirradiated coating; and the irradiated structure is selectively developed to remove a substantial portion of the unirradiated coating to form a patterned substrate.

13. The use according to any one of the preceding claims, wherein the metal and / or metalloid ketoic acid oxime salt and / or the ketoic acid oxime salt of the metal compound is such that the irradiated structure is heated at a temperature of about 50°C to about 150°C for 0.1 minute to about 20 minutes to form an annealed irradiated structure; and the annealed irradiated structure is selectively developed to remove a substantial portion of the non-irradiated coating to form a patterned substrate.

14. The use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing oxime salt of ketoacid and / or oxime salt of a metal compound is such that the irradiated structure is insoluble in an organic base and the non-irradiated coating is soluble in an organic base, so that the irradiated structure can undergo negative-tone imaging.

15. The use according to any one of the preceding claims, wherein the metal- and / or metalloid-containing ketoic acid oxime salt and / or the metal-containing ketoic acid oxime salt is used as a resist for producing a semiconductor device, comprising: a) exposing the resist to EUV or electrons; b) developing the resist film to form a resist pattern; c) etching the resist underlying layer film using the resist pattern; as well as d) manufacturing a semiconductor substrate using the resist film thus patterned and the resist underlayer film thus patterned.

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