Tin-based photoresist composition and method of making the same

Abstract

To provide high-resolution patterns.SOLUTION: Compositions comprising RqSnOm(OH)x(HCO3)y(CO3)z are disclosed, where R is (i) C1-C10 hydrocarbyl or (ii) heteroaliphatic, heteroaryl, or heteroaryl-aliphatic including 1-10 carbon atoms and one or more heteroatoms, with q=0.1-1, x≤4, y≤4, z≤2, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+y / 2+z)≤2. Methods of making a photoresist film comprising [(RSn)12O14(OH)6](OH)2 on a substrate are also disclosed. The photoresist film may be irradiated to form RqSnOm(OH)x(HCO3)y(CO3)z.SELECTED DRAWING: Figure 43

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of U.S. Provisional Application No. 62 / 982,599, filed February 27, 2020. The benefit of the earlier filing date is claimed, and is incorporated herein by reference in its entirety. (Statement on Government Support)

[0002] This invention was made possible by the National Science Foundation under award CHE-1606982. Made with U.S. Government support. The U.S. Government has certain rights in this invention. (Technical field)

[0003] The present disclosure relates to tin-based photoresist compositions and methods for making and patterning the compositions. It relates to a method of turning. Summary of the Invention

[0004] The present disclosure relates to tin-based photoresist compositions and methods for making and patterning the compositions. In one embodiment, the tin-based composition is RqSnOm(OH) x(HCO3)y(CO3)z, where R is: (i) a C1-C10 hydrocarbyl or (ii) a heteroaliphatic group containing 1 to 10 carbon atoms and one or more heteroatoms. , heteroaryl or heteroaryl-aliphatic, q=0.1 to 1, x≦4, y ≦4, z≦2, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+y / 2+ z)≦2. In another embodiment, the tin-based composition is RqSnOm(OH)x( HCO3)y(CO3)z, where R is (i) a C1-C10 hydrocarbyl or or (ii) heteroaliphatic, containing 1 to 10 carbon atoms and one or more heteroatoms; aryl or heteroaryl-aliphatic, q=0.1~1, x≦3.9, y ≦3.9, z≦1.95, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2 +y / 2+z)≦2. In certain embodiments, R is a C alkyl group, such as C1-C5 alkyl. In some examples, R is n-butyl. In any of the embodiments, x, y and z are selected from the group consisting of: (i) 0 <x≦3、(ii)0<y≦3 or (iii) 0 <z≦1.5、または(iv)(i)、(ii)および(iii)の It may have any combination of values.

[0005] The component may include a substrate and a membrane on at least a portion of the substrate, the membrane being as described herein. The disclosed tin-based composition comprises a film that can be patterned on a substrate. In some embodiments, (i) the membrane has an average thickness in the range of 2 to 1000 nm; or (ii) the film has a root mean square surface roughness of less than 1.5 nm; or (iii) Both i) and (ii).

[0006] In some embodiments, the method for preparing the tin-based photoresist composition comprises the steps of: exposing 3 to the atmosphere, thereby producing [RSnOH(HO)X]; where X is a halogen and R is defined as above, [RSnOH(HO)X 2] preparing a solution comprising 2 and a solvent; depositing the solution on a substrate; The solution and the substrate were heated to form a film of [(RSn)12O14(OH)6]X2 on the substrate. and then treating the membrane with [(RSn)12O14(OH)6]X2 in ammonia water. The substrate is contacted with the solution to produce a film having the composition [(RSn)12O14(OH)6]X2. and forming a film comprising [(RSn)12O14(OH)6]X2 on the substrate. Heating the deposition solution and substrate to form the SiO2 layer is carried out at temperatures ranging from 60 to 100°C for 1 h. This may involve heating for ~5 minutes.

[0007] In any of the above or below embodiments, R is a C1-C5 alkyl group, such as C1-C5 alkyl. In some embodiments, R is n-butyl. In any of the embodiments described below, the deposition solution and the substrate are heated to form [(RSn) The formation of a film comprising 12O14(OH)6]X2 can be achieved by heating at a temperature in the range of 60 to 100°C. This may include heating at 350° C. for 1 to 5 minutes.

[0008] In any of the above or below described embodiments, the method comprises the step of: 6] At least a portion of the film comprising (OH)2 is irradiated with an electron beam or irradiated with a 10 nm to 400 nm The membrane is irradiated with light having a wavelength in the range of 100 nm to 1000 nm to produce an irradiated membrane. In an embodiment, the irradiation is performed with light having a wavelength in the range of 10 to 260 nm; This involves the application of an electron beam at a dose of 125 μC / cm2 or more. In this embodiment, the irradiation is performed by irradiating the electron beam with a dose of 125 to 1000 μC / cm2. In any of the above embodiments, the irradiation may include irradiating [(RSn)12O14(O Cleavage of 10-100% of the R-Sn bonds in the irradiated part of the film with [H](OH) possible.

[0009] In any of the above or below described embodiments, the method may further include a post-irradiation treatment. In some embodiments, the method further comprises: (i) exposing the irradiated film to air at ambient temperature for at least three hours; or (ii) exposing the irradiated film to air at a temperature in the range of 100-200°C. and heating the irradiated portion of the irradiated film at 35° C. for 2 to 5 minutes. , adsorbs CO2 from the atmosphere and forms RqSnOm(OH)x(HCO3)y(CO3)z Here, q=0.1~1, x≦4, y≦4, z≦2, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+y / 2+z)≦2. In one embodiment, q=0. 1~1, x≦3.9, y≦3.9, z≦1.95, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+y / 2+z)≦2.

[0010] In some embodiments, a membrane comprising [(RSn)12O14(OH)6](OH)2 A portion of the is irradiated to form a patterned film, and the method comprises: Furthermore, the mixture is brought into contact with a solvent in which [(RSn)12O14(OH)6](OH)2 dissolves. The irradiated parts of the film contain dissolved [(RSn)12O14(OH)6](OH)2. The irradiated portions of the patterned film become less soluble for a time effective to dissolve the irradiated portions of the patterned film. do not.

[0011] A component comprising a substrate and a membrane on at least a portion of the substrate, as disclosed herein. The membrane produced by the method is also encompassed by the present disclosure. In one embodiment, the membrane is In some embodiments, (i) the membrane comprises: has a root mean square surface roughness of 0.8 nm or less, such as 0.5 nm or less, or (i i) Do the films have undetectable levels of Cl- as detected by X-ray photoelectron spectroscopy? or (iii) both (i) and (ii). In an independent embodiment, the membrane is qSnOm(OH)x(HCO3)y(CO3)z, where q=0.1-1, x ≦4, y≦4, z≦2, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+ In another independent embodiment, the film is RqSnOm(OH)x( HCO3)y(CO3)z, where q=0.1-1, x≦3.9, y≦3.9, z≦1.95, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+y / 2+ z)≦2.

[0012] The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: This will become more apparent from the detailed description below. [Brief description of the drawings]

[0013] [Figure 1] Ball and stick representation of (C4H9Sn)2(OH)2Cl4(H2O)2(Sn2); 1H and 119Sn NMR spectra show that the structure retains 2-heptanone. [Diagram 2] Figure 2A is a ball-and-stick representation of [(n-C4H9Sn)12O14(OH)6](OH)2(Sn12OH), and Figure 2B is small-angle X-ray scattering data showing that Sn2 was converted to Sn12OH. [Diagram 3] FIG. 13 shows XPS spectra of Sn2 film before and after base immersion. [Figure 4A] 1A-1C are atomic force microscope (AFM) images showing that deposition of Sn12 from the Sn2 precursor produces a much smoother film than direct deposition from the Sn12 precursor. [Figure 4B] 1A-1C are atomic force microscope (AFM) images showing that deposition of Sn12 from the Sn2 precursor produces a much smoother film than direct deposition from the Sn12 precursor. [Diagram 5]5A and 5B are diagrams showing temperature programmed desorption / mass spectrometry (TPD-MS) spectra of an Sn2 film and an Sn12OH film, respectively. [Figure 6] FIG. 4C shows ESI-MS electrospray ionization mass spectrometry spectra of the membranes of FIGS. 4A and 4B. [Figure 7] FIG. 13 shows the surface roughness of Sn2 films baked at selected temperatures after base immersion. [Figure 8] FIG. 13 shows the TPD-MS spectrum of the Sn2 film immediately after post-apply bake and NH3(aq) treatment. [Figure 9] Figure 9A is a TPD-MS spectrum tracking the desorption of H2O (8A) at low temperature versus time for the film, and Figure 9B is a TPD-MS spectrum tracking the desorption of CO2 (8B) versus time for the film. [Figure 10] Figure 10A is a TPD-MS spectrum showing that the low temperature desorption peak of HO (9A) is largely eliminated by baking at 140° C. for 3 min, and Figure 10B is a TPD-MS spectrum showing that the desorption peak of CO (9B) is largely eliminated by baking at 140° C. for 3 min. [Figure 11] 1 is a TPD-MS spectrum showing the main fragments of 1-butene. [Figure 12] 1 is a TPD-MS spectrum showing the main fragments of butane. [Figure 13] FIG. 1 is an illustration of the decomposition of an n-butyl ligand and subsequent electron impact ionization of the decomposition products. [Figure 14] Figure 2 shows the TPD-MS spectral signals associated with n-butyl desorption from samples exposed to 0, 300 and 1000 μC / cm2. [Figure 15] 13 is a graph showing loss curves for TPD-MS spectral signals associated with n-butyl desorption from samples exposed to 0, 300 and 1000 μC / cm2. [Figure 16] 1 is a graph showing film thickness as a function of irradiation dose. [Figure 17] Scanning electron microscope image of 25 nm lines written on a 100 nm pitch using an electron beam dose of 500 μC / cm2. [Figure 18] Reverse contrast cross-sectional cryo-STEM image of an exposed and undeveloped sample. [Figure 19] Cryo-EELS spectrum at 10 nm resolution of the sample in FIG. 17. [Figure 20] 1 is a graph showing film thickness as a function of irradiation dose for arrays aged 0.25, 3, 24 and 144 hours. [Figure 21] Images of dose arrays in vacuum (left) and air (right) after a 2 hour delay and then developed in acetone for 30 seconds. [Figure 22] Figure 22A is a TPD-MS spectrum of an unexposed and 1000 μC / cm2 exposed sample tracking the desorption of n-butyl with no delay time in air. Figure 22B is a TPD-MS spectrum of an unexposed and 1000 μC / cm2 exposed sample tracking the desorption of water with no delay time in air. Figure 22C is a TPD-MS spectrum of an unexposed and 1000 μC / cm2 exposed sample tracking the desorption of carbon dioxide with no delay time in air. [Figure 23] Figure 23A is a TPD-MS spectrum of H2O desorbed from a film exposed to 1000 μC / cm2 in air before and after a 10 day delay. Figure 23B is a TPD-MS spectrum of CO2 desorbed from a film exposed to 1000 μC / cm2 in air before and after a 10 day delay. Figure 23C is a TPD-MS spectrum of n-butyl (23C) desorbed from a film exposed to 1000 μC / cm2 in air before and after a 10 day delay. [Figure 24] Figure 13 is a TPD-MS spectrum of the butyl fragment after exposure to 1000 μC / cm2 after a 10 day delay in air. [Diagram 25]Figure 25A is a TPD-MS spectrum of n-butyl desorbed from a film exposed to 300 μC / cm2 after a one day delay in air. Figure 25B is a TPD-MS spectrum of water desorbed from a film exposed to 300 μC / cm2 after a one day delay in air. Figure 25C is a TPD-MS spectrum of carbon dioxide desorbed from a film exposed to 300 μC / cm2 after a one day delay in air. [Figure 26] Figure 26A is a TPD-MS spectrum of n-butyl desorbed from a film exposed to 500 μC / cm2 after a 6-day delay in air. Figure 26B is a TPD-MS spectrum of water desorbed from a film exposed to 500 μC / cm2 after a 6-day delay in air. Figure 26C is a TPD-MS spectrum of carbon dioxide desorbed from a film exposed to 500 μC / cm2 after a 6-day delay in air. [Figure 27] Figure 27A shows that n-butyl groups can be removed by heating the Sn12 film in air. Figure 27B shows that the n-butyl-deficient film absorbs H2O. Figure 27C shows that the n-butyl-deficient film absorbs CO2. [Figure 28] TPD-MS spectra of m / z=41 (n-butyl) for unexposed film, film exposed to UV light for 10 minutes, and film exposed to UV light for 10 minutes with a delay in air for 6 days. [Figure 29] TPD-MS spectra of m / z=18 (H2O) of a film exposed to UV light for 10 min and a film exposed to UV light for 10 min and delayed in air for 6 days. [Diagram 30] TPD-MS spectra of m / z=44 (CO2) for a film exposed to UV light for 10 min and a film exposed to UV light for 10 min and delayed in air for 6 days. [Diagram 31] FIG. 2 is a TPD-MS spectrum of a film exposed to UV light for 10 min and delayed in air for 6 days, showing CO2 fragmentation and undetected butyl signals. [Diagram 32]FIG. 1 illustrates the chemical reactions to induce dissolution changes between exposed and unexposed areas of a Sn12OH film. [Diagram 33] 1 is a graph showing that both H2O and CO2 are required to achieve dissolution contrast in an e-beam exposed Sn12 film. [Diagram 34] Figure 34A is a TPD-MS spectrum of n-butyl desorption from the film after irradiation at 1000 μC / cm2 and after post-exposure bakes (PEBs) at 140° C. and 180° C. for 3 minutes. Figure 34B is a TPD-MS spectrum of water desorption from the film after irradiation at 1000 μC / cm2 and after post-exposure bakes (PEBs) at 140° C. and 180° C. for 3 minutes. [Diagram 35] FIG. 13 shows thickness measurements of dose arrays exposed to no PEB, 100° C. PEB, 140° C. PEB and 180° C. PEB for 3 minutes. [Diagram 36] 13 is a TPD-MS spectrum showing that heating induces the desorption of n-butyl groups from Sn12 films at low temperatures. [Figure 37] TPD-MS spectra showing CO2 desorption from the three dose arrays of Figure 32 after exposure to 1000 μC / cm2 and 3 min PEB at 140°C and 180°C. [Figure 38] Figure 38A is a TPD-MS spectrum showing desorption of n-butyl following 3 min PEB at 320° C. either immediately or after a 6 day delay, and Figure 38B is a TPD-MS spectrum showing desorption of CO2 following 3 min PEB at 320° C. either immediately or after a 6 day delay. [Figure 39] 1 is a table of TPD-MS spectra of unexposed and unbaked exposed samples, or samples baked at 140° C. or 180° C. [Diagram 40] Figure 40A is a TPD-MS spectrum of an unexposed sample showing hydrolyzed Sn as a CO2 reaction site, and Figure 40B is a TPD-MS spectrum of an exposed sample after PEB showing hydrolyzed Sn as a CO2 reaction site. [Diagram 41]Figure 41A is a TPD-MS spectrum of n-butyl desorption after PEB at 180° C. Figure 41B is a TPD-MS spectrum of water desorption after PEB at 180° C. Figure 41C is a TPD-MS spectrum of carbon dioxide desorption after PEB at 180° C. [Diagram 42] Figure 42A is a TPD-MS spectrum after TGA of Sn12OH (42A) in N2. Figure 42B is a TPD-MS spectrum after TGA of Sn12OH (42B) baked in air. [Diagram 43] SEM image of 10 nm (horizontal) and 14 nm (vertical) lines on 60 nm pitch produced by Sn2 deposition, conversion to Sn12OH, e-beam exposure, post-exposure bake at 140 °C, and development in 2-heptanone. [Diagram 44] SEM images of line-and-space and dot patterns produced by Sn2 deposition, conversion to Sn12OH by NH3(aq) immersion, e-beam exposure, post-exposure bake at 180 °C, and development in 2-heptanone. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] An embodiment of a tin-based photoresist composition is disclosed. A method for testing the same is also disclosed.

[0015] I. Definitions and Abbreviations The following explanations of terms and abbreviations will better explain the present disclosure and will be of use to those skilled in the art in the practice of the present disclosure. As used herein, "comprises" means "includes" , the singular forms "a" or "an" or "the" are used unless the context clearly indicates otherwise. The term "or" includes plural references unless the context clearly dictates otherwise. “Compound” refers to any single element or combination of two or more of the alternative elements listed.

[0016] Unless otherwise explained, all technical and scientific terms used herein are The term "substitute" has the same meaning as commonly understood by a person skilled in the art to which the disclosure pertains. Methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention. Suitable methods and materials that may be used are described below. The materials, methods, and examples are merely illustrative. Other features of the present disclosure are described below for purposes of illustration and not limitation. This is apparent from the detailed description and claims that follow.

[0017] Disclosure of numerical ranges is intended to refer to each discrete point within the range, including the endpoints, unless otherwise specified. Unless otherwise indicated, the term "common" used in the specification or claims should be understood as meaning "common" or "non-common." All numbers used, representing amounts of ingredients, molecular weights, percentages, temperatures, times, etc., are given for illustrative purposes only. It should be understood that the term "about" is modified by the term "about" and therefore does not imply or expressly state otherwise. Unless expressly indicated or as otherwise appropriate, the context will be construed by one of ordinary skill in the art to have a more determinative structure. Unless otherwise understood, the numerical parameters set forth are intended to represent the desired properties sought and / or the intended application. It is an approximation that may depend on the limit of detection under standard test conditions / methods known to the manufacturer. The word "about" may be used to directly and explicitly distinguish an embodiment from the prior art discussed. Unless otherwise stated, the numerical values ​​of the embodiments are not approximations.

[0018] There are alternatives to the various components, parameters, operating conditions, etc. described herein. This does not imply that the alternatives are necessarily equivalent and / or perform equally well. Also, unless otherwise stated, the alternatives are not intended to be listed in order of preference. Definitions of common terms in chemistry are provided by John Wiley & Sons. Published by s,Inc.,Richard J. Lewis, Sr.(ed.). ,Hawley's Condensed Chemical Dictionary, 2016 (ISBN 978-1-118-13515-0). The compounds listed also include all isotopes of the atoms present in the compound, including deuterium, tritium, and argon. These may include, but are not limited to, 14C, 14T, and the like.

[0019] In order to facilitate review of the various embodiments of the present disclosure, the following explanations of specific terms are provided below. to provide.

[0020] Adsorption: The physical attachment or bonding of ions and molecules to the surface of another molecule. , as chemisorption or physisorption, depending on the nature and strength of the bond between the adsorbate and the surface. It can be characterized.

[0021] Aliphatic: Includes alkanes, alkenes, and alkynes, including their cyclic counterparts, as well as straight-chain and Substantially hydrocarbon-based, including linear and branched chain arrangements, and all configurations and structural isomers. A compound of the formula (I) or its radical (e.g., C6H13 for the hexane radical).

[0022] Alkyl: A hydrocarbon group having a saturated carbon chain. The chain may be cyclic, branched or unbranched. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, butyl ... These include ethyl, hexyl, heptyl, octyl, nonyl and decyl. The terms alkynyl and alkynyl refer to carbon atoms containing one or more double or triple bonds, respectively. It refers to a chain-containing hydrocarbon group.

[0023] Aromatic or aryl: An unsaturated cyclic hydrocarbon with alternating single and double bonds. Zene is a six-carbon ring containing three double bonds and is a typical aromatic compound. If the ring portion contains a heteroatom, the group is heteroaryl and not aryl. The aryl group is monocyclic, bicyclic, tricyclic or tetracyclic.

[0024] Arylaliphatic: Contains an aromatic portion and an aliphatic portion, and the point of attachment to the rest of the molecule is aliphatic. A group via a moiety.

[0025] Coating: A layer of material on the surface of a substrate. Synonymous with the word "film."

[0026] Film: A layer of material on the surface of a substrate. Synonymous with "coating."

[0027] Halogens and halides: As used herein, the terms "halogen (halo)" and "Halide" refers to Cl, Br or I.

[0028] Heteroaliphatic: Has at least one carbon atom and at least one heteroatom in the chain. That is, one or more carbon atoms are connected to an atom having at least one lone pair of electrons (usually Aliphatic or Heteroaliphatic compounds or groups may be substituted or unsubstituted, branched or unbranched, cyclic or and may be acyclic, and may be referred to as "heterocycle," "heterocyclyl," "heteroalicyclic," or "heterocyclic " group.

[0029] Heteroaryl: Having at least one heteroatom, i.e., one or more in the ring A carbon atom is attached to an atom that has at least one lone pair of electrons (usually nitrogen, oxygen, phosphorus, silicon, etc.). An aliphatic compound or group that is replaced by an alkyl group (carbon, aryl, aryloxy, or sulfur).

[0030] Heteroarylaliphatic: a group that contains an aromatic portion and an aliphatic portion and is attached to the rest of the molecule. The point of attachment of is through the aliphatic portion and the group contains at least one heteroatom. Unless otherwise specified, the heteroatom can be in the aromatic or aliphatic portion.

[0031] Hydrocarbyl: A monovalent radical derived from a hydrocarbon. A hydrocarbyl radical is a It may be linear, branched or cyclic and may be aliphatic, aryl or arylaliphatic.

[0032] Soluble: Capable of being molecularly or ionically dispersed in a solvent to form a homogeneous solution To be.

[0033] Solution: A homogeneous mixture of two or more substances. The solute (a minor component) dissolves in the solvent (the major component). Dissolve.

[0034] Sn2: (C4H9Sn)2(OH)2Cl4(H2O)2

[0035] Sn12OH (or Sn12): (n-C4H9Sn)12O14(OH)8

[0036] II. Photoresist Compositions The present disclosure relates to embodiments of photoresist compositions and methods of making the photoresist compositions. In one embodiment, the photoresist composition comprises RqSnOm(OH)x(HCO3 )y(CO3)z, where R is (i) a C1-C10 hydrocarbyl or (i i) Heteroaliphatic, heteroariphatic, heterocyclic ... aryl or heteroaryl-aliphatic, q=0.1~1, x≦4, y≦4, z≦2, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+y / 2+z)≦2 In another embodiment, the photoresist composition is RqSnOm(OH)x(HCO3)y (CO3)z, where R is (i) a C1-C10 hydrocarbyl or (ii) Heteroaliphatic, heteroaryl containing 1-10 carbon atoms and one or more heteroatoms Or heteroaryl-aliphatic, q=0.1-1, x≦3.9, y≦3.9, z≦ 1.95, m=2-q / 2-x / 2-y / 2-z and (q / 2+x / 2+y / 2+z) <= 2.

[0037] In some embodiments, R is a C1-C10 aliphatic, aryl, or aryl-aliphatic. In certain embodiments, R is a C1 The aliphatic chain may be linear, branched or cyclic. In some examples, R is a C1-C5 alkyl. Examples of R groups include methyl, ... ethyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl (2-methylpropyl) butyl, sec-butyl, tert-butyl, n-pentyl, 1 ,1-methylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpropyl ethylbutyl, 2-methylbutyl, 3-methylbutyl and 1-ethylpropyl, In some embodiments, R is heteroaliphatic, heteroaryl, or heteroaryl-aliphatic (wherein the heteroatoms are aryl and / or aliphatic moiety, the aliphatic moiety being the point of attachment to the Sn atom), It contains atoms and one or more heteroatoms. Suitable heteroatoms can include N, O, S and combinations thereof. The heteroaliphatic chain can be linear, branched or cyclic. In certain examples, R is n-butyl. In some embodiments, q = 0.1 to 1. In some embodiments, q = 0.3 to 1 or 0.5 to 1. In any of the foregoing or following embodiments, x ≤ 4. In one embodiment, x ≤ 3.9. In some embodiments, 0 < x ≤ 4, 0 < x ≤ 3.9 or 0 < x ≤ 3. In any of the foregoing or following embodiments, y ≤ 4. In one embodiment, y ≤ 3.9. In some embodiments, 0 < y ≤ 4, 0 < y ≤ 3.9 or 0 < y ≤ 3. In any of the foregoing or following embodiments, z ≤ 2. In one embodiment, z ≤ 1.95. In some embodiments, 0 < z ≤ 2, 0 < z ≤ 1.95 or 0 < z ≤ 1.5. In any of the foregoing or following embodiments, the photoresist composition can be deposited on a substrate as a film or layer. In some embodiments, the film has an average thickness in the range of 2 nm to 1000 nm and / or a root mean square (RMS) surface roughness of 1.5 nm or less. In certain embodiments, the average thickness is in the range of 2 to 750 nm, such as 2 to 500 nm, 2 to 250 nm, 5 to 250 nm, 10 to 100 nm or 10 to 50 nm, etc. The RMS surface roughness can be 1.5 nm or less, less than 1.5 nm, 1.2 nm or less, less than 1.2 nm, 1 nm or less or less than 1 nm, for example, 0.2 to 1.5 nm, 0.3 to 1 nm.

[0038] In any of the foregoing or following embodiments, q = 0.1 to 1. In some embodiments, q = 0.3 to 1 or 0.5 to 1. In any of the foregoing or following embodiments, x ≤ 4. In one embodiment, x ≤ 3.9. In some embodiments, 0 < x ≤ 4, 0 < x ≤ 3.9 or 0 < x ≤ 3. In any of the foregoing or following embodiments, y ≤ 4. In one embodiment, y ≤ 3.9. In some embodiments, 0 < y ≤ 4, 0 < y ≤ 3.9 or 0 < y ≤ 3. In any of the foregoing or following embodiments, z ≤ 2. In one embodiment, z ≤ 1.95. In some embodiments, 0 < z ≤ 2, 0 < z ≤ 1.95 or 0 < z ≤ 1.5.

[0039] In any of the foregoing or following embodiments, the photoresist composition can be deposited on a substrate as a film or layer. In some embodiments, the film has an average thickness in the range of 2 nm to 1000 nm and / or a root mean square (RMS) surface roughness of 1.5 nm or less. In certain embodiments, the average thickness is in the range of 2 to 750 nm, such as 2 to 500 nm, 2 to 250 nm, 5 to 250 nm, 10 to 100 nm or 10 to 50 nm, etc. The RMS surface roughness can be 1.5 nm or less, less than 1.5 nm, 1.2 nm or less, less than 1.2 nm, 1 nm or less or less than 1 nm, for example, 0.2 to 1.5 nm, 0.3 to 1 nm. 0.5nm, 0.3~1.2nm, 0.3~1nm or 0.3~0.75nm Such is the case.

[0040] III. METHODS OF MAKING AND PATTERNING PHOTORESIST COMPOSITIONS A smooth, dense film comprising the photoresist composition is desired. In some embodiments , by in situ formation of OH-stabilized butyltin dodecamer on the substrate, followed by the By forming a photoresist composition, a superior film is prepared.

[0041] RzSnO(2-(x / 2)-(x / 2)(OH)x, where 0<(x+z)<4, Organotin coatings having the general composition represented by the formula It has been shown to function well as known radiation patternable materials. Photoresists having sensitivity to ultraviolet (UV) radiation and extreme ultraviolet (EUV) radiation The use of organotin materials as materials was described by Meyers in "Organometallic c Solution Based High Resolution Pattern U.S. Patent No. 9,310,684, entitled "Integrating Compositions," and Meyers, "Organotin Oxide Hydroxide P alterning Compositions, Precursors, and The present invention is described in U.S. Patent No. 10,228,618, entitled "Patterning," , both of which are incorporated herein by reference.

[0042] The present disclosure relates to the preparation of an organotin precursor represented by the formula [RSnOH(HO)X] This can be prepared by reaction of RSnX3 with water, where X is a halo. In one embodiment, RSnX3 is a perihydride, and R is as defined above. When exposed to ambient air, [RSnOH(H2O)X2]2 is produced. [RS nOH(H2O)X2]2 is exposed to the atmosphere for a period during which RSnX3 is effective, e.g., 2 to 4 days. In some embodiments, X is Cl-. In the example, R is n-butyl.

[0043] Generally, organotin oxide hydroxide coatings are made from hydrolytically sensitive organotin precursor compositions. The aforementioned references also include spin-coating, Organotin oxide hydroxide coatings prepared by coating and vapor deposition techniques are described. The patternable organotin oxide hydroxide coatings are made up of one or more RnSnL4-n (n=1, 2) The hydrolyzate of the composition is dissolved in a suitable solvent, followed by spin coating. Furthermore, the vapor pressure of the RnSnL4-n composition is Because of the relatively high temperature, the hydrolyzable gas-phase precursor is introduced into a reactor sealed from the ambient atmosphere. Organotin oxide hydroxide coatings can also be produced by deposition techniques that involve hydrolysis as part of the deposition process. For example, one or more RnSnL4-n compositions can be mixed with H2O, H2O2 , O3, O2, CH3OH, or other small molecule gas-phase reagents, and then deposited on the desired substrate. Organotin oxide hydroxide compositions may be formed. Vapor deposition techniques include ALD (atomic layer deposition), PVD (physical vapor deposition), CVD (chemical vapor deposition), etc.

[0044] If solution deposition of an organotin coating is desired, [RSnOH(HO)X] and a solvent. Generally, the composition [RSnOH(H2O)X2]2 is Any solvent may be used that dissolves the amines and / or amines in the water. The choice of solvent will depend on its toxicity, flammability, volatility, viscosity, etc. and potential chemical interactions with other materials. Suitable solvents include, for example, 4-methyl-2-pentanol, propylene glycol, Alcohols such as polypropylene glycol methyl ether (PGME), ketones such as 2-heptanone, Esters such as propylene glycol monomethyl ether acetate (PGMEA), and / or mixtures thereof.

[0045] The concentration of the species in the solution may be evaluated on a Sn molar basis and generally depends on the desired physical properties of the solution and and the coating desired. For example, a more concentrated solution will generally have a higher A more concentrated solution generally results in a thicker film, whereas a less concentrated solution generally results in a thinner film. In some applications, such as coating, thinner films may be desirable. In a further embodiment, the Sn concentration is 0.005M to 1.4M, and in a further embodiment, 0.02M to 1.2M. M, which in additional embodiments may be 0.1 M to 1.0 M. Additional ranges are contemplated and will be recognized by one of ordinary skill in the art.

[0046] If deposition is required, the formation of [RSnOH(H2O)X2]2 can be achieved by, for example, isolating the This can be done by the gas phase reaction of RSnX3 with H2O in a separate chamber. The precursor RSnX3 was prepared by vapor, aerosol and / or direct liquid injection into the vaporization chamber. The fluid may be introduced into the chamber by means known to those skilled in the art, such as by using an inlet stream. Water is then introduced into the chamber through a separate inlet, either simultaneously with or after the introduction of the organotin precursor. The introduction of [RSnOH(H2O)X2]2 accelerates hydrolysis and forms a [RSnOH(H2O)X2]2 coating on the surface of the substrate. In some embodiments, the reaction is carried out at elevated temperatures relative to ambient. In some embodiments, the gas phase reaction is carried out multiple times until the desired film thickness is achieved. It is possible.

[0047] In either deposition method, the substrate can be any material of interest. The plates may include silicon, silica, ceramic materials, polymers and combinations thereof. In some embodiments, the substrate is a flat surface onto which the solution is deposited. In certain embodiments, the substrate is SiO2. Solution deposition includes spin coating, spray coating, dip coating, etc. The deposition may be performed by any suitable method, including but not limited to the deposition solution and the substrate. The reaction was carried out to produce a film with the composition [(RSn)12O14(OH)6]X2 on the substrate. The temperature and time are adjusted to effectively evaporate the solvent and leave [RSnOH(H2O)X2] 2 is chosen to convert it into the dodecamer [(RSn)12O14(OH)6]X2. In some embodiments, the substrate and deposition solution are heated to a temperature of 60-100° C. for 1-5 minutes. For example, the coating is subjected to a post-apply bake at a temperature of 80° C. for a period of 3 minutes. RSn)12O14(OH)6]X2 films have RMs of less than 0.5 nm or less than 0.4 nm. In some instances, the RMS surface roughness is about 0.3 nm. Surface roughness is determined by methods known in the art, such as atomic force microscopy. obtain.

[0048] Halides are subject to uncontrolled hydrolysis and / or chemical and structural heterogeneity. Halides can be used to overcome the undesirable effects of tin-based photoresists, allowing for uniform film formation. Therefore, it is beneficial to remove halides from the deposited film. Or in any of the embodiments described below, the halide is [(RSn)12O14(OH By contacting the film having [(RSn) 12O14(OH)6](OH)2. Conversion to a fluoride-containing film can be accomplished in other ways, but it is important to avoid contamination of the material with other metals. In general, the aqueous base solution should be metal-free, since it may be desirable to avoid Suitable aqueous base solutions include, for example, quaternary ammonium compounds (e.g. , tetramethylammonium hydroxide, tetrabutylammonium hydroxide, etc.), alkyl Amine compounds (e.g., diethylamine, ethylamine, dimethylamine, methylamine) In some embodiments, the aqueous base solution may include ammonia. The halides can be dissolved in dilute ammonia by short treatment with aqueous ammonia. Ammonia can be substantially removed from the membrane. mM, 5μM~1mM, 5μM~100μM, 5μM~50μM, 5μM~10μM, etc. For example, the short period of time may be 30 seconds to 15 minutes, 1 minute to It may be 30 seconds to 30 minutes, such as 10 minutes or 1 minute to 5 minutes. The chloride was chloride, and the film was deposited and post-coating baked with 10 μM NH3 (aq) Alternatively, NH3(aq) was removed by immersion in Paddy Field on the membrane for 3 min. The substrate can then be dried by spinning it on a spin coater to remove the water-soluble After alkali treatment, the [(RSn)12O14(OH)6](OH)2 film The membrane may be rinsed with water and dried by passing nitrogen over the rinsed membrane and / or Removal of the halides results in a slight reduction in the roughness of the film. Thus, in some embodiments, [(RSn)12O14(OH) 6](OH)2 films have an RMS surface roughness of less than 1.5 nm, 1 nm or less, or 0.8 nm or less. For example, the RMS surface roughness is 0.3 nm to 1 nm, 0.3 nm to 0.8 nm. or in the range of 0.3 nm to 0.5 nm.

[0049] In some embodiments, a precursor comprising [(RSn)12O14(OH)6](OH)2 A molecularly smooth film (e.g., RMS surface roughness less than 0.5 nm) is formed on the substrate. where R is as defined above. [(RSn)12O14(OH)6](OH The 2-layer film can be formed from a precursor comprising RSnX3, where X is a halide. In one example, the starting material is n-C4H9SnCl3 and the reaction is as follows: n-C4H9SnCl3(l) + air → [n-C4H9SnOH(H2O)Cl2]2 (s) 12[n-C4H9SnOH(H2O)Cl2]2(s)→[(n-C4H9Sn)1 2O14(OH)6]Cl2+22HCl(g)+H2O(s / g) [(n-C4H9Sn)12O14(OH)6]Cl2(s)+2NH4OH(aq) →[(n-C4H9Sn)12O14(OH)6](OH)2(s)+2NH4Cl(a q)

[0050] In any of the above or below embodiments, [(RSn)12O14(OH)6](O H)2 films are irradiated with electron beams or ion beams in the range of 10 nm to less than 400 nm, e.g. m~350nm, 10nm~300nm, 50nm~300nm, 100nm~300n m, 150 nm to 300 nm, or 200 nm to 275 nm. A photoresist film that can be patterned by irradiating a photoresist film with a In some embodiments, the irradiation is 100 nm, such as EUV light having a wavelength of 13.5 nm. Light with a wavelength in the range of 0 to 260 nm or a dose of 125 μC / cm2 or more is used. In a particular embodiment, the irradiation includes irradiating the electron beam with a 200-260 nm or In another embodiment, the method includes irradiating the surface of the substrate with light having a wavelength in the range of 250 to 260 nm. The irradiation is 125μC / cm2 or more, 200μC / cm2 or more, 300μC / cm2 or more. or irradiating the electron beam with a dose of 500 μC / cm2 or more. For example, ,Dose is 1000μC / cm2, 200~1000μC / cm2, 300~100 0μC / cm2 or in the range of 500~1000μC / cm2. R-Sn bonds (more specifically, C- In some embodiments, the cleavage of at least a portion of the R-Sn bonds occurs. 0-100%, 1-100%, 1-90%, 1-70% or 1-50% of RS n bonds up to 5%, up to 10%, up to 25%, up to 50%, up to 70%, up to 90% or In another embodiment, sufficient radiation is applied to cleave up to 100% of the R-Sn bond. 5~100%, 5~90%, 5~70%, 5~50%, 10~100%, 10~90 Sufficient irradiation is applied to cleave 10-70% or 10-50% of the This results in the detachment of the R group from the membrane.

[0051] In any of the above or below described embodiments, the photoresist film is Patterning was achieved by irradiating only selected parts of the [14(OH)6](OH)2 film. In some embodiments, the selected portion may be "written" with the electron beam. or by masking certain parts of the membrane and irradiating the unmasked parts. By this, irradiation is performed.

[0052] In any of the foregoing embodiments, the method may include post-irradiation treatment of the film. In some embodiments, post-irradiation treatment involves heating the irradiated film at ambient temperature (e.g., 20-25° C.). Expose the irradiated film to the atmosphere for at least 3 hours or heat it at a temperature between 100 and 200°C. In certain embodiments, the post-irradiation treatment includes heating in air at a temperature of 100° C. for 2 to 5 minutes. The treatment is carried out by subjecting the irradiated film to a temperature in the range of 140 to 180°C for 2 to 4 minutes, for example, at 140 to 180°C. In another embodiment, the post-irradiation treatment comprises heating the irradiated The membrane is then incubated for at least 3 hours, at least 5 hours, at least 12 hours, or at least 24 hours. , at least 2 days, at least 3 days, at least 7 days, or at least 10 days This involves simply exposing the material to air at ambient temperature for an extended period of time.

[0053] When the film is exposed to air for post-irradiation treatment, the irradiated areas of the film hydrolyze and the Sn-OH bonds in the film are Over time, the membrane absorbs more CO2 from the atmosphere. Although not wishing to be bound by the theory of synthesis, it is believed that the adsorbed CO2 is inserted into the Sn-OH bond. Then, the adjacent HCO3- and OH- groups are bonded to each other. can react to release HO, thereby forming simple carbonates (e.g., two adjacent Sn atoms) In some embodiments, the resulting membrane is has the general formula RqSnOm(OH)x(HCO3)y(CO3)z, where R, m, q, x, y and z are as defined above.

[0054] The presence of bicarbonate and carbonate groups in the membrane leads to the formation of [(RSn)12O14(OH)6](OH )2 membrane and 10-100% of the R-Sn bonds were broken [(RSn)12O14(OH)6 ](OH)2 membrane. The RqSn bridges adjacent to the Sn atoms, inhibiting solubility. Om(OH)x(HCO3)y(CO3)z is [(RSn)12O14(OH)6]( It is less soluble in certain solvents than [(RSn)12O14(O [H)6](OH)2 is readily soluble in certain ketones (e.g., 2-heptanone, acetone). However, RqSnOm(OH)x(HCO3)y(CO3)z is either insoluble or soluble. Thus, in some embodiments, the patterned film has a low [(RSn) When the film is exposed to a solvent that dissolves 12O14(OH)6](OH)2, the irradiated area of ​​the film is transformed into a patterned Without dissolving the irradiated part of the irradiated film, [(RSn)12O14(OH)6](O H)2. The unexposed areas of the photoresist layer were then treated with 2-heptanone to form a patterned photoresist layer. for a few seconds to a few minutes, for example, 15 seconds to 2 minutes, 15 seconds to 1 minute, or 15 to 45 seconds. In a particular example, the patterned photoresist layer is removed by 2- Contact with butanone was allowed for 30 seconds.

[0055] (IV. Component Parts) The components are made by embodiments of the disclosed methods. In some embodiments, The component comprises a substrate and a film on at least a portion of the substrate, where the film is a [(RS n) 12O14(OH)6](OH)2, where R is defined as above. (i) a root-mean-square surface roughness of 0.8 nm or less; (ii) as detected by X-ray photoelectron spectroscopy; or (iii) having both (i) and (ii). do.

[0056] In any of the foregoing or following embodiments, the membrane may be patterned as disclosed herein. and a patterned structure comprising a substrate and a film on at least a portion of the substrate. a membrane comprising RqSnOm(OH)x(HCO3)y(CO3)z, where q, x, y, z and m are as defined above.

[0057] In any of the foregoing embodiments, the substrate can be any material of interest. Typical substrates include silicon, silica, ceramic materials, polymers and combinations thereof. In some embodiments, the substrate includes, but is not limited to, a substrate having a film disposed thereon. In certain embodiments, the substrate comprises a flat or substantially flat surface on at least a portion of the substrate. The substrate is SiO2. EXAMPLES

[0058] V. Working Examples material As previously described by Luijten (Recueil des Trav aux Chimiques des Pays-Bas 1966,85(9):87 3-878), (C4H9Sn)2(OH)2Cl4(H2O)2(Sn2) crystals, -C4H9SnCl3(l) (Alfa Aesar, 96%) in a fume hood The mixture was placed in a crystallizing dish and left for 3 days until Sn2 crystallized. (n C4H9Sn) 12O14(OH)8(Sn12OH) crystals were prepared by Eychenne-Baron et al. As previously described (J Organometallic Chem 1998, 56 7(1):137-142).

[0059] Thin Film Coating The solution deposition precursor for Sn2 and Sn12 was 2-heptanone (Alfa Aesar, 99%), 0.14 g and 0.12 g per mL, respectively, were dissolved in 0.45 μm PT The solution was prepared by filtering through a FE syringe filter. Valley Microelectronics, Inc.) substrate. 0 nm SiO2 was dissolved in acetone, isopropyl alcohol, and 18.2 mQ-cm H The precursor solution was added to a 2.54x2.54cm2 wafer, washed with 2O and annealed at 800°C for 15 min. The sample was then spun at 2000 RPM for 30 seconds on a hot plate preheated to 80°C. The substrate was then transferred to a stand and baked for 3 minutes.

[0060] Thin films prepared from Sn2 were subjected to alkaline treatment. These films were prepared as-deposited and after 8 h. Immediately after PAB at 0°C, the plates were completely immersed in 10 μM NH3(aq) for 3 min. After treatment, the membrane was rinsed with 18.2 MΩ·cm H2O and dried with an N2 gun.

[0061] Exposure and Contrast Curves Sn12OH films prepared from Sn2 were used for the patterning experiments. 30 with Quanta 3D Dual Beam SEM and NPGS software The experiment was carried out using a 20 kV electron beam with a linearly increasing dose to draw a square array. The contrast curve was created by plotting the image. A post-exposure ageing or bake step in 3000 mL of 2-heptanone was applied. The dose array was developed by covering for 0 s and drying the sample with a N2 gun. Using a Woolam MX-2000 ellipsometer fitted with a lobe, each square Thickness measurements were collected in the form of a plot of thickness as a function of dose or log dose. Exposure to UV light emitted two wavelengths at λ = 254 and 185 nm. This was done using the Digital UV Ozone System (Novascan). Ta.

[0062] XPS X-ray photoelectron spectroscopy (XPS) was collected using Physical Electronics A (PHI)5600 MultiTechnique UHV system was used. The base pressure of the chamber was less than 2x10-10 torr. Using Kα radiation (hν=1486.6 eV, 300 W, 15 kV), Ag 3d, C l 2p, Sn 3d and Sn MNN Auger spectra were obtained. An electron analyzer pass energy of 3.5 eV and an emission angle of 45 degrees were used. Spectral peak fits were performed using Gaussian-Lorentzian lineshapes and Shirley backgrounds. The results were determined using a Casa XPS (Frisch et al., Gauss (ian 16, Revision A.03, 2016). The atomic concentration is measured using an X-ray source and an electron detector. Using published sensitivity coefficients specific to the XPS system used at 90 degrees between the detector and the detector, (Perdew et al., Phys. Rev. Lett. 1997, 78(7) :1396).

[0063] AFM RM using Bruker Veeco Innova SPC in tapping mode Atomic force microscopy was performed to measure the S roughness values. Nanoscope Ana lysis1.5 was used for background subtraction and noise equalization.

[0064] TPD TPD-MS was performed on a Hiden Analytical TPD Workstation. The membrane was cut into 1x1 cm2 samples and placed in the UHV chamber of the device ( The sample was heated to 800°C at a linear heating rate of 30°C / min. The MS was operated at an electron ionization energy of 70 eV and an emission current of 20 μA. Selected mass-to-charge (m / z) ratios of each sample were acquired for 150 ms and 5 min, respectively. Observations were made in MID mode at 0 ms dwell time and stabilization time.

[0065] SEM Scanning electron microscope images taken at 30k resolution on a Quanta 3D Dual Beam SEM. The electron beam was collected using a V

[0066] ESI-MS The extracted membrane solution was analyzed using an Agilent 6230 electrospray ionization mass spectrometer. The solution was introduced into the spectrometer at a flow rate of 0.4 mL / min using a syringe pump. To promote the evaporation of the solution, N2(g) was added at 325 °C and 241 kPa. The flow rate was 8 L / min. The capillary voltage was set to 3500 V and the skimmer to 65 V. The RF octopole was set to 750 V. The data was analyzed using the fragmentation voltage The power was set at 30 V and collection was performed in both positive and negative ionization modes.

[0067] TEM and EELS TEM images were taken on an FEI Titan 80-200 TEM using a 200 keV beam. EELS analyses were performed using a GaT The measurements were performed on Titan using a Tridiem energy analyzer. The single-tilt cryoholder Gatan 626 used for the EELS experiment The temperature remained stable at -170 °C throughout the experiment. One tilt axis was used to tilt the sample to Si<11 0> The sample was oriented very close to the zone axis and perpendicular to the beam.

[0068] (Results and Discussion) Atomically smooth Cl-free thin films from Sn2: Sn2 has four Cl ligands (Figure 1). Two Sn atoms have hydroxyl groups. Two Cl ligands and one H2O molecule are associated with each Sn atom. A -butyl group is also attached to each Sn atom. The Sn2 solution precursor is then spin-coated. After deposition with butyltin 12-mer [(n-C4 The membrane is converted to the chloride salt H9Sn)12O14(OH)6]Cl2(Sn12Cl). It is very smooth with a root mean square (RMS) roughness of 0.3 nm. , an undesirable component of tin-based photoresists. It is Uncontrolled hydrolysis can affect pattern fidelity at various steps of the process. This creates the opportunity for dissolution and the formation of chemically and structurally inhomogeneous films. The membrane was converted to a Cl-free membrane by replacing it with OH-. OH-stabilized butyltin 12-mer [(n-C4H9Sn)12O14(OH)6](OH)2(Sn12OH, Fig. 2A and 2B) have been reported previously, based on the stronger nucleophilic character of OH-. It was hypothesized that OH- was exchanged for Cl-.

[0069] Therefore, the Sn12Cl film was immersed in 10 M NH3(aq) for 3 min immediately after deposition and heated at 80 °C. The XPS (X-ray photoelectron spectroscopy) spectrum in the upper part of Figure 3 shows the results of the base immersion. Strong Cl 2p1 / 2 and 2p3 / 2 signals were observed in the pre-immersion deposition and post-PAB films. The lower spectrum shows that when immersed in NH3(aq), the Cl signal disappears from the background. This result indicates that the Cl in the film was assimilated by immersion in NH3(aq) for 3 min. This is interpreted as meaning that - was removed and a 12-mer OH- salt was produced.

[0070] After the NH3(aq) bath, surface images of the membrane were collected with an atomic force microscope (AFM) (Figure 4A). and Figure 4B). The RMS roughness of the resulting film decreased slightly from 0.32 nm to 0.45 nm. The surface was shown to be smooth at the atomic level. However, the smooth film morphology of the film prepared from Sn2 was not significantly deteriorated. As seen in Figure 4A, when Sn12 is deposited from the Sn2 precursor, the Sn12 precursor This produces a much smoother film than direct deposition from the Sn2O3 solution. Atomically smooth Cl-free patternable n-butyltin oxide from solid crystals This is a summary of chemical reactions to isohydroxo thin films.

[0071] Deposition and PAB: 6[(n-C4H9Sn)Cl2(OH)(H2O)]2→[(n-C4H9Sn)1 2O14(OH)6]Cl2(s)+22HCl(g)+H2O(s / g) (Formula 1)

[0072] Base Soak: [(n-C4H9Sn)12O14(OH)6]Cl2(s)+2NH4OH(aq) →[(n-C4H9Sn)12O14(OH)8](s)+2NH4Cl(aq) (Formula 2)

[0073] The film coated from Sn2 was Sn12O on the wafer after PAB and base immersion. To confirm the generation of H speciation, bulk crystals of SnOH were prepared. The deposition of the Sn2 and Sn12OH solution precursors was performed by evaporation and The process parameters were as follows: Sn2 film (Sn12Cl) was ionized in NH3(aq) for 3 minutes. The only difference was the number of digits per sigma.

[0074] Table 1 shows the chemical composition measured from the XPS data and the calculated formula for Sn12OH. The composition of the films fabricated from Sn2 is summarized below. The molecular concentration matches within 3% of the film fabricated from Sn12OH, and the composition is consistent with that predicted by the molecular formula. agreed within 2%.

[0075] [Table 1]

[0076] Figures 5A and 5B show temperature programmed desorption (TPD) spectra collected for both films. The desorption mass, peak signal temperature, and relative peak intensity were indistinguishable between the two membranes. The film was extracted by immersion and dissolution in methanol, and the A solution was prepared to evaluate speciation. Electrospray ionization mass spectrometry (ESI-MS) was identical (Figure 6), with approximately 1250 and 250 Two major peaks were found, centered around a mass-to-charge ratio (m / z) of 0. These The peaks correspond to the +2 and +1 ions of the parent SnOH dodecamer. The complex lines are the result of -OH and -OCH3 ligand exchange within the 12-mer cation.

[0077] The ESI-MS spectra of the two samples showed that -OH was partially exchanged with -OCH3 ligands. These are distinguished by varying degrees of peak splitting that occurs due to the exchange of Since the source of the methoxo ligand is introduced first and only into the system, the dissolution process in methanol is Thus, the splitting of the characteristic peaks can only occur during the speciation process on the wafer. It does not represent the difference between

[0078] XPS, TPD, and ESI-M show that the on-wafer This provides complementary evidence for Sn12OH speciation. It aids in the conversion of Sn2 to Sn12OH based on base immersion.

[0079] Organotin photoresists are typically applied and irradiated during lithography. These materials have low surface roughness to create high resolution patterns. After the NH3(aq) treatment, bake for an additional 3 minutes and then The roughness behavior of the films baked at 140 to 180°C was evaluated. Figure 7 shows that the films baked at 140 to 180°C had a similar surface roughness to the initial one. The data show that the RMS roughness remains at about 0.75 nm despite the The films applied with typical PAB and PEB processing temperatures are as high as those required for high resolution photoresist materials. It was suggested that the wafer would continue to exhibit excellent roughness of 0.75 nm or less, which is the required condition. The speciation above is the same, but all radiation experiments show that Cl produced from Sn2 The Sn2 process was carried out on a film that did not contain Sn12OH (RMS = 1.3 The results showed that the surface roughness of SnO was 0.2 nm, whereas that of SnO was 0.45 nm. When the film directly processed from H was baked, the surface morphology changed to 4.43n by 140 °C. It rapidly coarsened to m.

[0080] Patterning Chemistry Non-exposed membrane to establish baseline: TPD-MS was performed to study the thermally induced desorption spectra from Cl-free thin films prepared from Sn2. The spectrum shown in Figure 8 is the product of H2O, CO2, and n-butyl ligands. reveal three major abscission signals.

[0081] Figure 8 shows three low intensity signals at temperatures below 200°C. The water peak at 75°C is , which is due to the desorption of HO from the structure. This peak was observed after 11 days of aging in air (Figure 9A This is because the membrane slowly absorbs atmospheric H2O(g) during this period. The CO2 peaks at 75°C and 200°C indicate that the metal The interaction between the oxide surface and CO2(g) is expected, which may lead to the desorption of weakly adsorbed CO2. The relative intensities of these two CO2 desorption peaks vary irregularly over time in the atmosphere. This behavior is due to the dynamic transport of CO2 weakly adsorbed on the metal oxide surface. This can be attributed to the movement of the film. By adopting a soft bake in air at 140°C for 3 minutes, This significantly reduced the three low-temperature H2O and CO2 desorption peaks (Figure 10). The peaks below 200°C represent the desorption of molecular and weakly bound H2O and CO2 adsorbates. It was concluded that:

[0082] The most intense desorption phenomenon from the TPD spectra in Figure 8 occurs at 400°C, and various organic frames are The peaks related to the thermally induced Sn-C bond accompanied by H removal or extraction were revealed. The cleavage occurs in the form of 1-butene (C4H8) (Figure 11) or n-butane (C4H10) ( From the known fragmentation patterns of both products, Upon ionization dissociation, the propyl fragment was expected to give the most intense signal. Figure 13 shows that the propyl chain [m / z = 41 (C3H5), m / z = 43 (C3H7)] is The following shows how to represent the 1-butene and n-butane products, respectively.

[0083] 1-butene (C4H8) (Figure 10) and n-butane (C4H10) (Figure 12) are ionic The patterns in the ionization systems are similar, making it difficult to determine relative abundance without standardization of the mass spectrometer. However, the expected intensity of m / z=43 is 100% for n-butane and 1 In -butene, the concentration is essentially 0%. The experimental spectrum shows a substantial peak at m / z=43. Therefore, the Sn-butyl pyrolysis of these films resulted in the production of n-butane and It is well shown that this resulted in the production of both 1-butene and other decomposition products. The peaks from m / z=41 onwards were the most intense, and therefore the relative abundance of the butyl group in the membranes after various treatments was confirmed. It is used to represent the concentration of

[0084] At 400°C, peaks at m / z=18 and 44 were also observed. At this temperature, m / z=44 can be attributed to either CO2 or C3H8 (a product fragment of butane). However, M / z=18 is a product of the fragmentation of C4H8 or C4H10. Therefore, it is possible that the TPD experiment induced Sn-butyl pyrolysis with HO as a by-product. Finally, the weak CO2 peak detected at 600 °C was assigned to water. The lines are indicated by asterisks in Figure 8.

[0085] Exposed film A 1x1cm2 film was irradiated with an electron beam and immediately subjected to TPD analysis. , which is consistent with the sample dimensions required for TPD analysis. n-Butyl desorption (m / z=41) from a sample exposed to 1000 (red) μC / cm2 The intensity of the desorption signal decreases with increasing dose. It was suggested that the n-butyl content decreased with increasing amount of ethanol (Figure 15). The curves are zero-order, with aligned leading edges, separated trailing edges, and offset peak temperatures. The three indices of desorption kinetics are shown in Fig. 1. The TPD measurements showed that electron beam irradiation caused the formation of Sn-C bonds. The bond is broken, and the n-butyl ligand is released from the gas, which causes the organic ligand in the film to It was found that the concentration decreased.

[0086] The TPD data in Figure 14 summarizes the decrease in the C3H5 signal with increasing exposure dose. The inset shows the exponentially decayed signal with a fit of R2 = 0.98. The film thickness from lipometry also showed an exponential decrease as a function of dose (Figure 1 6) (R2 = 0.97). As a result, these data indicate that the probability of Sn-C bond cleavage is It is shown that the concentration of Sn-C bonds, i.e., butyl groups in the film, is simply proportional to the concentration.

[0087] The detachment of the butyl ligand and the associated change in film thickness and density are related to the exposed areas of the film. It has been shown that the non-exposed regions can be imaged and characterized by electron microscopy (EM). Using an electron beam at 30 kV with a dose of 500 μC / cm2, two SnO Thin lines (approximately 25 nm) were written on the H film with a pitch of 100 nm. Post-exposure bake (PEB) at 140 °C for 3 min to confirm via scanning electron microscope (SEM). ) and then immediately developed with 2-heptanone for 30 seconds. (Figure 17)

[0088] The second film was not developed. The patterned film is very sensitive to heat. 2. Extract Electron Transparent Lamella for EM Analysis Using Cryo-Focused Ion Beam Milling Prior to milling, a layer of chromium was deposited, followed by a protective coating of C and Pt. All of these were performed via deposition. ) images and carbon electron energy loss spectroscopy (EELS) data. This prevented additional beam damage.

[0089] FIG. 18 shows a reverse contrast cross-sectional cryo-STEM image of an exposed and undeveloped sample. From bottom to top, the layers are SiO2 substrate (light grey), exposed Sn12OH (black) corresponds to the protective chrome layer (dark grey). The periodic dark areas with a spacing of about 75 nm correspond to These represent the exposed areas of the resist. These are the line spacings observed in the fully developed pattern. Clearly, the cryo-induced ionization in combination with the high atomic number contrast STEM enables direct imaging of normally invisible latent images in inorganic photoresists This allows for a unique approach to

[0090] Figure 19 shows a Sn12OH film exposed parallel to the substrate, performed at 10 nm resolution. The data shows three linescans of carbon EELS through the sample. There are three distinct reductions in carbon due to the exposed areas. The lowest carbon in each line is The counts correspond to a loss of 50% of the carbon, which corresponds to 50% of the butyl ligands. Similar results were obtained with carbon EELS point scans. These data are Further evidence that irradiation breaks Sn-C bonds, leading to the desorption of organic species from the films. Provide evidence.

[0091] Considering the difficulties in FIB sample preparation and cryo-EM measurement, approximately 50% of the butyl ligand was This loss of 10% is comparable to the approximately 40% loss observed with TPD. Statistical variations in deposition and processing of the crystals, as well as cryo-FIB milling and cryo- This may be due to potential carbon loss during STEM analysis.

[0092] Retardation after atmospheric exposure: Electron beam exposure was performed in the vacuum chamber of the SEM following the procedure detailed in the Experimental Section. After writing, the sample was removed from the vacuum environment and -The arrays were aged in air before being developed in heptanone for 30 seconds. One array was left undeveloped. Figure 20 shows the thickness of the array after 0.25, 3, 24 and 144 hours. as a function of dose. The undeveloped array maintains 100% of the pre-development film thickness. The delay time required for the

[0093] All exposed pads of samples subjected to a 0.25 hour delay were simply dissolved in 2-heptanone. There was no difference in the dissolution rate between the exposed and unexposed areas of the film. After 24 hours, a decrease in dissolution rate was observed for high dose pads (>200μC / cm2). After a delay of 100 μC / cm2, dissolution begins at around 125 μC / cm2 and saturates at around 200 μC / cm2. , where the pad thickness is equal to that of the latent image control. When aging is continued for more than 24 hours, The change in sensitivity was small. Maximum contrast after aging in air for 24 hours The difference in dissolution rate was 5.1. The delay time between exposure and development has a large effect on the difference in dissolution rate. It is clear that...

[0094] Slow changes in aging may be due to exposure alone or to reactions with the atmosphere. To determine whether this occurs, we aged the arrays in vacuum for 2 hours and in air for 2 hours each. A direct comparison was made with the aged array. Figure 21 shows that only the air-retarded sample exhibited a This shows that upon development, a clear contrast was created between the exposed and unexposed areas. From the observations, it is believed that the dissolution rate can be changed by changing one or more atmospheric components [CO2(g), H2 It was concluded that absorption of [O(g), O2(g)] was necessary. The arrays were developed with only 100 μl of solubility in 10 μl of 10 ... Since a long exposure time (>24 hours) is required, acetone was used as the developer in this experiment. Heptanone outperforms all other reported development stages due to the higher contrast it provides. It was used for the

[0095] Two 1x1cm2 samples were exposed to 1000μC / cm2 electron beam irradiation. After that, one sample was immediately transferred to the ultra-high vacuum (UHV) chamber of the TPD instrument, and the other One sample was aged in air for 10 days. The transfer from SEM to TPD took approximately 15 days. This maximizes the reaction product on the membrane and therefore the desorption signal of TPD-MS. To maximize the Selected.

[0096] 22A-22C show the results for the unexposed film and from the exposed and immediately transferred sample. n-Butyl, H2O and CO2 elimination signals, respectively. All three species are 100 μC / cm2 exposure, showing an overall decrease in desorption.

[0097] Figures 23A-23C show the results of the immediate and air-aged samples, respectively, exposed to 1000 μC / cm2. Desorption of H2O (23A), CO2 (23B) and n-butyl (23C) from the ion exchange sample Figure 23A shows that a 10-day delay in air results in a higher intensity of HO desorption. The low-temperature signal of water desorption from the structure (Figure 9A) indicates that H Due to the increase in the concentration of 2O, the temperature shifted from 75°C to 90°C. A higher signal was expected, indicating that these films adsorb HO from the atmosphere ( Figure 9A). The strong H2O desorption represented by the line between 200 and 300 °C is consistent with the aging of the film. showed that the hydroxylated membrane was more extensively hydroxylated than the unaged membrane. The aged film absorbed more water. This was because the aged film absorbed more water at 75 to 150°C. This is evident from the higher H2O desorption signal.

[0098] Figure 23B identifies the CO2 signal for the same two samples. The aged exposed samples showed significantly higher CO2 A desorption signal was observed. The area under the exposure curve was approximately 4 times that of the unaged curve. These signals are due to the 2× CO2 adsorbent rather than the weakly bound CO2 adsorbent (Figure 9B). The signals in Figure 23B that desorbed only at temperatures above 00°C were HCO3- and CO32- Related to.

[0099] Finally, the exposure curves in FIG. 23C show that a 10 day delay in air significantly reduces the onset of butyl desorption. The peak shifted from 300 to 175 °C, and the peak signal shifted from 400 to 350 °C. The same trend was observed for m / z = 43 (C3H7), 56 (C4H8) and 58 ( This was also observed for other organic fragments (C4H10) (Figure 24). The areas under the pores agree with each other within 5% and are consistent with the actual concentration of ligand remaining after aging. These spectra indicate that outgassing of organics occurs during the exposure process. and that the chemical environment of the remaining butyl ligands is not sensitive to aging in the atmosphere. The results show that the n-butyl elimination and the increase in temperature from 400 to 350°C caused The shift of both peak signals upon hot H2O desorption (Figure 23A) indicates that hot water desorption is This further demonstrates that it is a by-product associated with decomposition.

[0100] Although weaker intensities were observed, the same trend was observed at 300 μC / cm2 and 500 μC / cm2. m2 exposure, followed by a delay of 1 or 6 days in air (Figures 25A-25C, 26A~26C).

[0101] 27A to 27C show the removal of n-butyl groups by heating the Sn12 film in air. Next, these n-butyl-deficient films were compared with electron beam exposed films. In a similar manner, H2O (27B) and CO2 (27C) are absorbed to produce hydroxides, bicarbonates, and and produces carbonates.

[0102] The TPD experiment consisted of immediate and atmospherically delayed The experiment was repeated for 10 samples. The samples were exposed for 10 minutes. One sample was immediately exposed to UHVTPD chamfers. One sample was transferred to the laboratory and the other sample was aged in air for 6 days. The data shows butyl loss from the exposed sample compared to the signal from the light sample. The m / z=41 peak is completely removed. This indicates that all Sn-C bonds have been broken. This means that the exposure dose was sufficient to break down the ligand product. No butyl-related desorbed masses were detected, indicating complete removal rather than degradation fragments trapped by the membrane. It guarantees removal.

[0103] Figure 29 shows the H2O desorption spectra from unaged and aged samples. The CO2 desorption is shown in Figure 30. Again, the atmospheric age After ionization, significantly higher desorption signals are observed: m / z = 44 (CO2+) and The identical peak shape of 8 (CO+) provides further evidence that m / z=44 indeed represents CO2. Provides certainty (Figure 31).

[0104] Carbon dioxide reacts with the Sn-O bonds of tin alkoxides and with tin hydroxides on metal oxide surfaces. It is shown that the carbonate is smoothly inserted into the Sn-O bond of the SnO core. There have been many reports on the use of di-n-butyltin oxide for efficient C It is also stated to be an O2 scavenger.

[0105] While not wishing to be bound by any particular theory of operation, the chemical reaction in Figure 32 is The electron beam or UV exposure contributes to the dissolution of Sn The -C bond is cleaved, facilitating the elimination of the butyl ligand as butane or butene. When the material is introduced into the atmosphere, the Sn sites in the exposed areas are hydrolyzed, increasing the concentration of Sn-OH-. Over time, the film absorbs CO2, which is inserted into the Sn-OH bonds to form bicarbonate. Next, adjacent bicarbonates react to release HO and form simple carbonates. The formation of Sn carbonate can inhibit dissolution by condensation through the CO32- bridge. The formation of n-linked terminal carbonate ligands HCO3- is also significantly more favorable than n-butyl ligands. The properties of carbonates vary widely, which can affect their solubility. It can bring about trust.

[0106] The gradual change in dissolution rate (Figure 20) is due to the gradual CO2 adsorption and therefore the gradual bicarbonate dissolution. This is a direct result of the formation of acid salts and carbonates. Since the following was observed, it was hypothesized that the formation of carbonate species weakens the Sn-C bond ( Figure 23C).

[0107] FIG. 33 shows the results of a method for achieving dissolution contrast in a Sn12 film exposed to an electron beam. We demonstrate that both H2O and CO2 are necessary for the induction of oxidative stress. The samples were analyzed in air (baseline), in a desiccator (HO-deficient environment), and in a wet globe. Expose in CO2 depleted environment for 24 hours and develop in 2-heptanone for 30 seconds. The exposed films were then annealed in a CO2-free, humid environment (wet glove box). When aged, it did not show any dissolution contrast.

[0108] M / z = 32, corresponding to O2, was not detected above the baseline in any of the TPD experiments. Furthermore, when the dose array was delayed for 24 hours in an isolated O2(g) environment, No pattern was observed upon development (elimination of n-butyl (34A) and water (34B) These data indicate that, at least by itself, O2(g) suggested that radiation-induced responses were not completed, and therefore its involvement was excluded.

[0109] Post Exposure Bake Figure 35 shows the results for no PEB, 100℃ PEB, 140℃ PEB and 180℃ PEB for 3 minutes. The thickness measurements of the dose array exposed to the 3 min PEB are shown. All samples were immediately developed in 2-heptanone for 30 seconds so that there was no delay time.

[0110] Unbaked dose arrays, when removed from vacuum and immediately developed, are prone to dissolving. The sample baked at 100°C had no contrast at 300μC / c. The dissolution rate decreased at doses near 140°C and 180°C. The pre-development thicknesses of these devices were 260 μC / cm2 and 200 μC / cm2, respectively. The data shows that when T ≥ 140°C and PEB is used, the data can be etched at an exposure dose of less than 300 μC / cm2. Ensure that sufficient energy is provided to produce insoluble products and avoid lag times. FIG. 36 shows that n-butyl groups are desorbed from the Sn12 film at lower temperatures upon heating. This indicates that.

[0111] Repeat the electron beam exposure followed by TPD, this time with a larger exposed area of ​​1x1cm2. A PEB step was added to the area. Three samples were exposed at 1000 μC / cm2 and immediately after exposure. Only two of them were subjected to PEB at 140°C and 180°C for 3 min. They are then quickly placed in the TPD's UHV chamber to minimize exposure to air. The desorption spectrum after PEB was nearly identical to that after a long delay in air. The same was observed.

[0112] Figure 37 shows the CO2 desorption from the three samples. The signal increases with increasing PEB temperature. The PEB temperature increases significantly, suggesting an increase in the concentration of carbonate species. It also shows that -butyl elimination shifts to a lower peak temperature and HO elimination increases (Figure After PEB at 320°C for 3 min, 80% of the butyl ligands were Both of these trends were observed for samples aged for long periods at room temperature in air. This is consistent with the results of

[0113] Figures 35 and 37 were developed immediately after exposure in vacuum due to the relatively low carbonate concentration. This suggests that the exposed samples do not result in differential dissolution. When carbonate species of a certain degree are observed, dissolution is effectively inhibited. The PEB process is simply Provides sufficient energy to activate the CO2(g) reaction with hydrolyzed Sn, It was concluded that it accelerates the reaction rate.

[0114] To determine whether Sn-bound -OH- is the active site for carbonate formation, To do this, both the unexposed and exposed samples were heated to 180°C in air. The desorption spectra were compared before and after heating. Baking the unexposed sample substantially The effect is to bake out the intact Sn12OH species. represents the baking of butyl-deficient Sn atoms that are hydrolyzed upon introduction into the atmosphere.

[0115] Figures 39 and 40A-40B show the desorption of all three species (n-butyl, H2O, and CO2). It is shown that the release spectrum changed dramatically upon baking in air for only the exposed sample. As mentioned above, exposed films baked at 180°C showed increased CO2 desorption, which increased the amount of carbon in the film. This suggests an increase in the nate group. When an unexposed sample was baked, the desorption spectrum before and after heating Therefore, the Sn-OH- sites absorbed CO2(g) and converted it to bicarbonate. It was concluded that thioacids and carbonates were formed.

[0116] Both HCO3- and CO32- were reacted with HCl after aging in air or at temperatures up to 180°C. It was hypothesized that these nanoparticles form in the film during baking (Figures 23B, 37, and 41A-4). 1C). The CO2 peak in the TPD spectrum between 200 and 400 °C is due to the H The 2O signal was also observed and was attributed to the decomposition of Sn bicarbonate. Since no H2O peak was detected, the CO2 peak was probably due to the decomposition of Sn carbonate. Represents.

[0117] Thermogravimetric-mass spectrometry was performed to mimic partial exposure to bulk SnOH powder. GA-MS was performed with SnOH in N to establish a baseline (Figure 42A). The Sn12OH is then baked in air to decompose some of the butyl ligands, thereby preventing exposure to light. (Figure 42B). The same trend was observed for the bulk powder.

[0118] Patternability – Proof of Concept: Based on all the above observations, Sn12OH is Lithographic patterning was performed using PEB and 2-heptanone for 30 seconds. 3 is a 10 nm line with a 60 nm pitch in the horizontal direction and a 14 nm line with a 60 nm pitch in the vertical direction. The difference in line width between the horizontal and vertical lines is due to the beam splitting in two directions. This is due to the difference in the step size. conversion to Sn12OH by electron beam exposure, post-exposure baking at 180 °C, and 2- Line and space patterns produced by the process of development with heptanone and This is an SEM image of a dot pattern.

[0119] (Conclusion) A method has been developed to produce Cl-free, atomically smooth Sn12OH films. We present a model system to elucidate the chemical processes that contribute to its high-resolution patterning capability. TPD-MS was used to characterize the chemical makeup of films after exposure to radiation, aging in air, and baking. The chemical changes of TPD were analyzed by cryo-STEM and cryo-EELS measurements. The spectrum shows that radiation breaks the Sn-C bond, resulting in the release of butane and butene. When introduced into the atmosphere, the exposed film reacted with H2O(g) and CO2 (g) Absorbs and forms hydroxides, bicarbonates, and carbonates. Aged at room temperature In the membrane, limited evidence of extensive condensation was found, where OH-, HCO3- and The exchange of n-butyl ligands for CO3 and CO32- caused a large interfacial area between the exposed and unexposed areas of the film. A post-exposure bake with HO( g) and CO2(g) absorption, producing a dissolution contrast similar to that of aging. The amount of additional crosslinking that may occur upon baking requires further study.

[0120] Considering the many possible embodiments to which the principles of the disclosed invention may be applied, the illustrated The embodiments are merely preferred examples of the present invention and are not to be construed as limiting the scope of the present invention. It should be recognized that the scope of the present invention should not be construed as being limited to the scope of the present invention. Rather, the scope of the present invention is defined by the claims. Therefore, all that comes within the scope and spirit of these claims is intended to be the invention. It is claimed as follows.

Claims

1. 1. A method for removing chloride from an organotin film, comprising contacting a film of an organotin composition comprising (i) chloride and (ii) R—Sn, Sn—O, and Sn—OH bonds with a base to remove chloride from the film, wherein R is (i) C １ ~C １０ hydrocarbyl or (ii) heteroaliphatic, heteroaryl or heteroaryl-aliphatic containing 1 to 10 carbon atoms and one or more heteroatoms.

2. The organotin composition is [(RSn) １２ O １４ (OH) ６ ]Cl ２ The method of claim 1 , comprising:

3. 2. The method of claim 1, wherein R is n-butyl.

4. 10. The method of claim 1, wherein the base comprises a quaternary ammonium compound, an alkylamine compound, or ammonia.

5. 5. The method of claim 4, wherein the base is aqueous ammonia.

6. 6. The method of claim 5, wherein the aqueous ammonia solution has a concentration ranging from 5 μM to 100 mM.

7. 10. The method of claim 1, wherein contacting the membrane with the base comprises contacting for 30 seconds to 30 minutes.

8. After contacting the membrane with the base, the membrane is reacted with a compound of the formula [(RSn) １２ O １４ (OH) ６ ](OH) ２ The method of claim 1 , comprising the composition represented by

9. 10. The method of claim 1, wherein the film has a root-mean-square surface roughness of less than 1.5 nm after contact with the base.

10. 10. The method of any one of claims 1 to 9, further comprising rinsing the membrane with water after contacting with the base.

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