Light acid propellant
阅读说明：本技术 光酸发生剂 (Light acid propellant ) 是由 J·W·撒克里 S·M·科利 J·F·卡梅伦 P·J·拉博姆 O·昂格伊 V·杰恩 A· 于 2011-11-30 设计创作，主要内容包括：光酸发生剂。一种以式(I)所示的光酸发生剂化合物：G<Sup>+</Sup>Z<Sup>-</Sup>(I),其中G具有式(II)<Image he="134" wi="463" file="DDA0002194101880000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中在式(II)中,X是S或I,每个R<Sup>0</Sup>通常连接到X,且独立的为C<Sub>1-30</Sub>烷基；多环或单环C<Sub>3-30</Sub>环烷基；多环或单环C<Sub>6-30</Sub>芳基；或包括前述至少之一的组合,G具有大于263.4g/mol的分子量,或G具有小于263.4g/mol的分子量,且一个或多个R<Sup>0</Sup>基团进一步连接到相邻的R<Sup>0</Sup>基,a是2或3,其中当X是I时,a是2,或当X是S时,a是2或3,且式(I)中的Z包括磺酸阴离子、磺酰亚胺或磺胺。光致抗蚀剂和涂敷薄膜也包括光酸发生剂和聚合物,以及使用所述光致抗蚀剂的电子设备的形成方法。(Light acid propellant.One kind is with light acid propellant compound shown in formula (I): G + Z ‑ (I), wherein G has formula (II) Wherein in formula (II), X is S or I, each R 0 It is typically connected to X, and is independently C 1‑30 Alkyl；Polycyclic or monocycle C 3‑30 Naphthenic base；Polycyclic or monocycle C 6‑30 Aryl；Or including at least one aforementioned combination, there is G molecular weight or G greater than 263.4g/mol to have the molecular weight for being less than 263.4g/mol, and one or more R 0 Group is connected further to adjacent R 0 Base, a are 2 or 3, wherein when X is I, a is 2, or when X is S, a is 2 or 3, and the Z in formula (I) includes sulfonic acid anion, sulfimide or sulfanilamide (SN).Photoresist and coating film also include light acid propellant and polymer, and the forming method of the electronic equipment using the photoresist.)
1. a kind of photoresist, the photoresist includes with formula (I) compound represented, quencher and including photosensitive official The polymer that can be rolled into a ball:
G+Z- (I)
Wherein G+It is
Wherein X is S or I,
When X is I, R' is (i) lone electron pair, alternatively, R' is (ii) monocycle or the polycyclic C of singly-bound when X is S6-30Aryl or C7-20Alkyl-aryl-group；
And the Z in formula (I)-Including sulfonic acid anion, sulfimide or sulfonamide,
The quencher right and wrong can photodegradation alkali.
2. photoresist according to claim 1, wherein in formula (I) compound represented, Z-It is C1-30Alkyl group sulphur Acid, C3-30Cycloalkylsulfonic acid, C1-30Fluorinated alkanes base sulfonic acid, C3-30Fluoro cycloalkylsulfonic acid, C6-30Aryl sulfonic acid, C6-30Fluoro virtue Base sulfonic acid, C7-30Alkarylsulphonic acid, C7-30Fluoro alkarylsulphonic acid, C1-30Fluorinated alkanes sulfimide, C2-30Fluoro cycloalkanes sulphonyl Imines, C6-30Fluorinated aryl sulfimide, C7-30Alkaryl sulfonyl imines, C7-30Fluoro alkaryl sulfonyl imines or including aforementioned At least one combination.
3. photoresist according to claim 1, wherein in formula (I) compound represented, Z-It is:
4. photoresist according to claim 1, wherein the polymer includes first containing acid-sensitive functional group poly- Close unit and the second polymerized unit including alkali solubility functional group.
5. the copolymer of claim 4, wherein first polymerized unit is formed by following molecular formula compounds represented:
Or including at least one aforementioned combination, wherein R4It is H, F, C1-6Alkyl or C1-6Fluoro-alkyl, second polymerized unit The alkaline soluble monomers as shown in following molecular formula are formed:
Or including at least one aforementioned combination, wherein R5It is H, F, C1-6Alkyl or C1-6Fluoro-alkyl.
6. a kind of coating substrate, the substrate include:
(a) there is one or more layers substrate to be imaged on the surface thereof；With
(b) the photo-corrosion-resisting agent composition layer described in claim 1 on one or more layers to be imaged.
7. a kind of method for forming electronic equipment, which comprises
(a) photo-corrosion-resisting agent composition layer described in claim 1 is applied in substrate；
(b) make photo-corrosion-resisting agent composition layer patterned exposure in exciting radiation；With
(c) photoresist layer of exposure is made to develop to provide camegraph.
Technical field
The cross reference of related application
The application be on November 30th, 2010 submit U.S. Provisional Application No.61/418,196 non-provisional application, Its content is fully incorporated and refers to herein.
Background technique
When the compound of generation acid (referred to herein as " light acid hair is decomposed in exposure in ultraviolet region wavelength (i.e. < 300nm) Raw agent ") it is the basis that chemistry amplifies " chemistry amplification " deprotection of polymer in photo-induced etching agent or crosslinking in microelectronic applications. Observed mainly include low molecular weight organic molecules such as isobutene (from overactivity energy photoresist in photoresist Agent) and acetaldehyde (from low-activation energy photoresist) these photoresists decomposition product, and from light acid The decomposition product of propellant, the photoresist are used for the imaging tool (stepping operated under wavelength such as 248nm and 193nm Device (stepper)) in.The degassing of these materials is coatable and corrodes optical device.
The effect for having taken up measure limitation decomposition product degassing such as cleans optical device and/or in optical device and light It causes to include sacrifice screen or filter between resist coating.However, industrial trend is smaller and smaller be less than The higher resolution of the line width of 45nm is developed in considerably shorter wavelength (such as deep UV region (EUV) of 13.5nm) work Make and have the new tool of senior reflection optical device, so the degassing for needing to control in photoresist again is horizontal.
Various photoresists are had studied in EUV exposure process for the contribution of the degassing of photoresist. Pollentier (" uses integrated EUV resist degassing/Pollution Study (the Study of EUV used of the device of EUVL technique Resist Outgassing/Contamination for Device Integration using EUVL ), Processes " Pollentier, I., J.Photopolym.Sci.Technol., 2010, the 23rd (5) volume, 605-612 Page) it has been found that sample is exposed in sealing room, the degassing of several photoresists is tested by residual gas analysis (RGA), and After exposure by gas phase/mass spectral analysis atmosphere, several main decomposition products of photoresist after tested include low molecule Compound such as benzene and diphenyl sulfide are measured, reason is the decomposition product of light acid propellant (if the light acid propellant of research is trifluoro Loprazolam triphenylsulfonium).Particularly, the volatile decomposition products including sulphur need to consider, because these materials may not be able to It is effectively removed from optical device, when the ionic light acid propellant based on triphenylsulfonium cation has satisfactory high sensitivity Property simultaneously provides quick film speed (< 10mJ/cm in photoresist2) when, more become problem.
Summary of the invention
Overcome by specific embodiment with light acid propellant compound shown in formula (I) above-mentioned and in the prior art Other defects:
G+Z- (I)
Wherein G has formula (II)
Wherein in formula (II), X is S or I, each R0It is typically connected to X, and is independently C1-30Alkyl；Polycyclic or monocycle C3-30 Naphthenic base；Polycyclic or monocycle C6-30Aryl；Or including at least one aforementioned combination, G has the molecule greater than 263.4g/mol Amount or G have the molecular weight less than 263.4g/mol, and one or more R0Group is connected further to adjacent R0Base, a are 2 Or 3, wherein a is 2 when X is I, or when X is S, a is 3, and the Z in formula (I) includes sulfonic acid, sulfimide or sulfonamide Anion.
In other specific embodiments, photoresist includes light acid propellant compound and gathering containing acid-sensitive functional group Close object.
In other specific embodiments, coating substrate (substrate) includes (a) having on the surface thereof to be imaged One or more layers；(b) the photo-corrosion-resisting agent composition layer on one or more layers to be imaged.
In other specific embodiments, the method for forming electronic equipment is included (a) the photoresist of claim 9 The coating of composition is applied in substrate；(b) make photo-corrosion-resisting agent composition layer Imagewise exposure in exciting radiation；(c) make The photoresist layer of exposure is developed to provide camegraph.
Specific embodiment
New light acid propellant disclosed herein (is herein PAG) when being exposed to actinic radiation, has low degassing characteristic, spy It is not to be exposed under radiation (such as electron beam, x-ray and the deep ultraviolet (EUV) with the 13.5nm wavelength) radiation of advanced lithographic printing When being used in the photoresist of light.Light acid propellant isCation has high photosensitivity, but these for actinic radiation The decomposition product of PAG has relative to general such as diphenyl iodine sunThe PAG of ion and triphenylsulfonium cation is photic anti- Erosion agent composition, exposure and the same terms of processing reduce.
It uses hereinRefer to iodineOr sulfonium cation." substituted " also used herein refers to including taking Dai Jiru halogen (i.e. F, Cl, Br, I), hydroxyl, amino, mercapto, carboxyl, carboxylate, amide groups, itrile group, mercapto, sulphur Base (sulfide), disulfide group (sulfide), nitro, C1-10Alkyl, C1-10Alkoxy, C6-10Aryl, C6-10Aryloxy group, C7-10Alkane Base aryl, C7-10Alkyl-aryloxy or at least one aforementioned combination.It is understood that being appointed according to disclosed in this paper structural formula Meaning group or structure can also be replaced in this way, and unless otherwise noted or these substitutions can significantly, adversely influence resulting structures Required characteristic.Moreover, " (methyl) acrylate " that text is used both had referred to acrylate or methyl acrylate, and it is not limited to this A bit, unless otherwise noted.
PAG disclosed herein is based on anionic-cationic structure, wherein the cation is that aryl replaces(i.e. two take For iodineOr three replace sulfonium) cation, the aryl replacesCation or molecular weight are greater than triphenylsulfonium cation, Such structure, wherein the heteroaryl structure replaced be connected further to for example includingOne in the heterocycle structure of ion Or multiple adjacent aryl, or the part as fused aromatic ring system.
Therefore PAG disclosed herein includes the compound with formula (I):
G+Z- (I)
Wherein G is that aryl replacesCation and Z are based on suitable strong acid (such as sulfonic acid or sulfonic acid imide anion) The anion of conjugate base
G has formula (II)
Wherein in formula (II), X isHetero atom and preferred S or I.Each R0It is typically connected to X, and is independently C1-30Alkane Base；Polycyclic or monocycle C3-30Naphthenic base；Polycyclic or monocycle C6-30Aryl；Or including at least one aforementioned combination.
Cationic G (being indicated with formula (II)) can have greater than 263.4g/mol molecular weight (i.e. be greater than triphenylsulfonium sun from Son (C6H5)3S+Molecular weight, herein also referred to as TPS cation).When G has the molecular weight greater than TPS cation, it is possible to understand that Be aryl substituent further in structure be greater than TPS, and the decomposition product of G therefore on molecular weight be greater than corresponding TPS Decomposition product.
Optionally, the G in formula (II) can have the molecular weight less than 263.4g/mol, and condition is one or more R0Base into One step is connected to adjacent R0Base.For example, being typically connected toThe adjacent phenyl group at the center hetero atom (I or S) can further pass through Singly-bound or C1-20Bridge group (such as methylene or substituted methylene), hetero atom (such as O, S, N etc.) or longer bridge joint Group (such as ethylidene, trimethylene, o- or-phenylene etc.) be mutually connected to relative to phenyl andBetween hetero atom Link position ortho position (when an aryl is phenyl, and adjacent aryl is different (such as naphthalene, anthryl etc.), can be with It is meta position, aligns or individually by different link positions).In this embodiment by this method, the substitution of ortho position two is obtained Biphenyl (biphenyl) thick five-membered ring, wherein biphenyl is commonly attached toHetero atom.
Also in formula (II), a is 2 or 3, wherein when X is I, a is 2, or when X is S, a is 2 or 3.For it is above-mentioned can To be further understood that, R0Group number can both refer to independent R0Group can also refer to the half R for being connected to X0Group, wherein Two R0Group is usually interconnected and is connected with X, or is connected to the one third group of X, wherein three R0Group is mutually connected It connects and is connected with X.
Preferred PAG compound includes that wherein G is formula (III), (IV) or (V):
Wherein X is I or S, each R3、R4、R5And R6The independent singly-bound for being attached to adjacent phenyl group, hydroxyl, itrile group, halogen, C1-10Alkyl, C1-10Fluoroalkyl, C1-10Alkoxy, C1-10Fluoroalkyloxy, C6-20Aryl, C6-20Fluoro aryl, C6-20Aryloxy group, C6-20 Fluorine aryloxy group, C1-20Alkylidene (alkylene) or C1-20Alkylene oxide group (alkoxylene)；P is 2 or 3, wherein when X is I, p It is 2, and when X is S, p is 2 or 3；Independent with each q and r is integer from 0 to 5, s and t it is independent be whole from 0 to 4 Number.It is to be further understood that in formula (III), when X is S and p is 2, at least one R2It is the C for connecting aryl to X1-20Alkylene Base (alkylene) or C1-20Alkylene oxide group (alkoxylene).In formula (V), Ar1And Ar2It is further independently C10-30It is thick It closes or singly linked polyaromatic, the polyaromatic includes the structure based on naphthalene, xenyl, anthryl, phenanthryl, double aryl oxides And the combination (such as phenyl-naphthalenyl, xenyl-naphthalene) including these structures；And R7It is lone electron pair (X is I) or C6-20 Aryl (X is S) and can further comprise that substituent group is such as usually those of disclosed above.
Example PAG cation G includes following structures in formula (I):
Wherein X is S or I, on condition that X is I, R' is lone electron pair, and R is C1-10Alkyl, C1-10Fluoroalkyl, C1-10Alkoxy or C1-10Fluoroalkyloxy, when X is S, R' is C6-30Aryl, C6-30Arlydene or C7-20Alkyl-aryl-group, each R " is independent be H, OH, halogen, C1-20Alkyl, C1-20Fluoroalkyl, C1-20Alkoxy, C1-20Fluoroalkyloxy, C3-20Naphthenic base, C3-20Fluorine naphthenic base, C6-20Aryl, C7-20Alkyl-aryl-group or it is independent including at least one aforementioned combination and each R " ' be H, C1-20Alkyl, C1-20Fluoroalkyl, C1-20Alkoxy, C1-20Fluoroalkyloxy, C3-20Naphthenic base, C3-20Fluorine naphthenic base, C6-20Aryl, C7-20Alkyl-virtue Base or including at least one aforementioned combination.
Z in formula (I) includes the anion of sulfonic acid, sulfimide or sulfonamide.Preferably, Z is C1-30Alkyl sulfonic acid, C3-30Cycloalkylsulfonic acid, C1-30Fluoroalkyl sulfonic acid, C3-30Fluoro cycloalkylsulfonic acid, C6-30Aryl sulfonic acid, C6-30Fluorinated aryl sulphur Acid, C7-30Alkarylsulphonic acid, C7-30Fluoro alkarylsulphonic acid, C1-30Fluoroalkane sulfimide, C2-30Fluoro cycloalkanes sulfimide, C6-30Fluorinated aryl sulfimide, C7-30Alkaryl sulfonyl imines, C7-30The anion of fluoro alkaryl sulfonyl imines or including before The combination at least one stated.
The Exemplary anionic Z of formula (I) includes having those of following molecular formula:
PAG disclosed herein is preferred in the photoresist in EUV lithographic printing, when being exposed to EUV radiation, with The radiation of other wavelength, which is compared, has satisfactory especially absorption and resolution characteristic.For example, in addition in the region EUV (about 12- 14nm, the special launch wavelength used be 13.4-13.5nm) in launch wavelength outside, EUV radiation source can longer wavelength swash Hair, light acid propellant may be sensitive to the wavelength, such as in 248nm and/or 193nm (and for DUV and 193nm lithographic printing In KrF and ArF swash state laser excitation wave band).PAG disclosed herein is high sensitivity for EUV, other for these Emission lines, known in the prior art as " frequency is outer " (OOB) launch wavelength, it is preferably minimum, i.e., lower than commonly used in these wavelength The PAG of (248 or 193nm), such as triphenylsulfonium (TPS) PAG or bis- (2-methyl-2-phenylpropane base) iodinePAG.PAG disclosed herein for 248 or 193nm radiation preferably has OOB photonasty, is reported as at EUV and 248 or 193nm conditions of exposure, uses PAG preparation photoresist dosage to the ratio (E of clarity (dose-to-clear)0, with mJ/cm2Report), it is less than Or it is equal to 1.5, especially less than or it is equal to 1.3, more especially less than or is equal to 1.1, then especially less than or equal to 1.0.
It can be by being used to prepare iodineOr the suitable conventional method of sulfonium PAG prepares PAG.Iodine disclosed hereinLight acid Propellant is usually by any one preparation in several different methods.For example, double aryl iodidesSalt can be by by donor residues The C that group replaces6-30The simple condensation of aryl (such as sulfuric acid and acetic anhydride) and iodate such as Potassiumiodate under strong acid/dehydration conditions with Obtain the iodine that double aryl replacePrepared by salt precursor, the electron donating group such as alkyl, alkenyl, hydroxyl, ether, Its aromatic radical (phenyl such as replaced by electron donating group (such as phenoxy group)) and other similar groups.It is symmetrical with high yield preparation With asymmetric substituted iodineUseful other methods of salt precursor are included in sodium perborate (NaBO3) and acetic acid in the presence of aoxidize Iodo aromatic hydrocarbon, and with the secondary aryl of iodo or Koser's reagent (aryl hydroxyl iodine with donor residuesToluene fulfonate, i.e., Ar-I (OH) (OTs)) condensation.
Sulfonium optical acid generating agent is usually prepared by the following method, if sulfenyl biaryl compound is (i.e. by preferably giving as above-mentioned The C that electron group replaces6-30The diaryl sulphoxide of aryl preparation) and other groups such as C6-30Aryl compound or C1-30Alkyl is (excellent Selecting has electron donating group) it is reacted in the presence of suitable dehydrated reagent or lewis acid (such as sulfuric acid or Eaton's reagent), with Promote the condensation reaction of sulfenyl group and aryl or alkyl compound, generates cation.It is understood that two virtue of sulfenyl The condensation reaction of based compound may be the intramolecular condensation with substituent group.
Pass through the iodine of any these methods preparationOr sulfonium salt can further using the salt of suitable acid or acid, acid imide or Amine carries out transposition anion exchange and obtains iodine accordingly with required anion (such as above-mentioned Z)Or sulfonium salt.Preferably, In Anion used in transposition exchange is the salt of sulfonic acid or its salt or sulfanilamide (SN) or sulfimide.
PAG compound disclosed above can be used for preparing photoresist.In a specific embodiment, photoresist packet Include PAG compound and the polymer including acid-sensitive functional group.
The polymer can be not restricted for for any polymer in photoresist；For example, being used to prepare light The polymer of resist is caused, the resist can be used for chemical-amplification positive or negativity under DUV (248nm) and 193nm exposure Photoresist.It is preferable, however, that the polymer is the polymer for being used to prepare photoresist, the resist is utilized The actinic radiation that advanced micro planographic plate printing uses is exposed, such as x-radiation, electron beam or above-mentioned EUV herein.It is understood that Be, used in the photoresist component of context " polymer " can for a kind of polymer, multiple polymers or one kind or Multiple polymers and other combinations for one of photoresist or multiple polymers.
Preferred polymer includes the combination of two or more polymerized units, and every kind provides polymer different characteristics. Preferably, polymer includes the first polymerized unit comprising acid-sensitive functional group, and the including alkali solubility functional group second polymerization are single Member.First polymerized unit can be by the C with acid-sensitive functional group10-30Acid-sensitive enester (olefinic ester) monomer is formed.It is acid-sensitive Group can be naphthenic base, multi-ring alkyl or aromatic radical, have the tertiary alkyl center for being connected to enester.First polymerized unit can be excellent Choosing is formed by the compound with following molecular formula:
Or including at least one aforementioned combination, wherein R4It is H, F, C1-6Alkyl or C1-6Fluoro-alkyl.Preferred exemplary list Body includes the R in above structure4For-CH3The monomer of group (i.e. (methyl) acrylic ester).
Second polymerized unit can be by the C with alkali solubility functional group10-30Alkali solubility allyl ester monomer is formed.The alkali solubility official Can roll into a ball to be the enester of naphthenic base or multi-ring alkyl with hexafluoroisopropanol base and optional the second polar group such as hydroxyl, or Person has the vinyl aromatic or enester of phenolic hydroxyl group or hexafluoroisopropanol base as the aromatic radical of alkali solubility functional group.Second can The polymerized unit preferably alkaline soluble monomers as shown in following molecular formula are formed:
Or including at least one aforementioned combination, wherein R5It is H, F, C1-6Alkyl or C1-6Fluoro-alkyl.
It is understood that all polymer containing the first and second above-mentioned polymerized monomers are and light disclosed herein acid Propellant is consistent.It is understood that other monomeric units can further comprise in the polymer, such as deriving from C8-20Vinyl aromatic (co) Monomer of perfume base, such as styrene, 4-Vinyl phenol etc.；C including norbornene and substitution norbornene7-20Cycloolefin, C4-20Olefin(e) acid acid anhydride such as maleic anhydride, itaconic anhydride, citric anhydride etc.；Other C10-30(methyl) acrylate monomer, including have The monomer of lactone function, such as α-(gamma butyrolactone) (methyl) acrylate, and including at least one aforementioned combination.
Other than PAG compound and polymer, photoresist may include additive, including such as photodegradation alkali and table Face activating agent.It may also comprise other additives, such as decomposition rate inhibitor, emulsion, others PAG.It is described photic anti- Erosion agent component is dissolved in for assembling and applying in solvent.
Photoresist may include photodegradation alkali.The basic matterial (the preferably carboxylate of photodegradation cation) for including The mechanism for neutralizing and decomposing the acid that group generates by acid is provided, limits the dispersion of photogenerated acid, therefore mention in photoresist Improved control is supplied.
Photodegradation alkali includes photodegradation cation, and is preferred for preparing those of PAG, such as with weak acid (pKa > 2) C1-20The anion of carboxylic acid matches.These illustrative carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexyl Carboxylic acid, benzoic acid, salicylic acid and other carboxylic acids.Illustrative photodegradation alkali includes cation shown in following structures and yin The combination of ion, wherein cation is triphenylsulfonium or one of the following:
Wherein R is independently H, C1-20Alkyl, C6-20Aryl or C6-20Alkaryl, and anion is
RC (=O)-O-, or-OH,
Wherein R is independently H, C1-20Alkyl, C1-20Alkoxy, C6-20Aryl or C6-20Alkaryl.Other photodegradation alkali include Based on the alkali of nonionic photodegradation chromophore, such as 2- nitrobenzyl and perfume base of resting in peace.Illustrative light alkali propellant is adjacent nitre Base Benzylcarbamate.
Optionally, or in addition, other additives may include for the quencher of non-photodegradation alkali, such as based on hydroxide, Those of carboxylate (carboxylate), amine, imines and amide.Preferably, these quenchers include C1-30Organic amine, imines Or amide, or can be highly basic (such as hydroxide or alkoxide) or the C of weak base (such as carboxylate)1-30Organic quaternary ammonium salt.Example The quencher of property includes amine, such as Troger's alkali, bulky amine such as diaza-bicyclo endecatylene (diazabicyclo undecene, ) or diaza-bicyclo nonene (diazabicyclononene, DBM), or the ionic quencher such as hydrogen including season alkylammonium salt DBU Aoxidize tetrabutylammonium (TBAH) or lactic acid tetrabutylammonium.
Surfactant includes fluoro and non-fluorinated surfactant, and preferably nonionic.Exemplary fluoro it is non-from Sub- property surfactant includes perfluor C4Surfactant such as FC-4430 and FC-4432 surfactant is purchased from 3M company；With POLYFOX PF-636 of the fluoro-diol such as from Omnova, PF-6320, PF-656 and PF-6520 fluoro surfactants.
Photoresist further comprises the solvent that component in photoresist is applied to suitable for dissolution, dispersion and painting.Show Example property solvent includes methyl phenyl ethers anisole, the alcohols including ethyl lactate, 1- methoxy -2- propyl alcohol and 1- ethoxy -2- propyl alcohol, including acetic acid is just The esters of butyl ester, 1- methoxy -2- propyl-acetic acid ester, methoxy (ethoxy) propionic ester, ethoxyethoxy propionic ester, including cyclohexanone and 2- heptan The ketone of ketone, and the combination including at least one aforementioned solvents.
Photo-corrosion-resisting agent composition disclosed herein includes the PAG less equal than 50wt%, and especially 1 arrives 40wt%, More specifically 1 30wt% is arrived, then especially 2 arrive 20wt%, the total weight based on solid.Photo-corrosion-resisting agent composition packet disclosed herein The polymer that 99wt% is arrived less equal than 50 is included, especially 55 arrive 95wt%, more specifically 60 arrive 90wt%, then especially 65 arrive 90wt%, the total weight based on solid.
Light alkali propellant can be present in photoresist with 0.01 to 5wt% amount, and in particular 0.1 arrives 4wt%, more especially It arrives 3wt%, the total weight based on solid for 0.2.Surfactant can be included the wherein amount for arriving 5wt% with 0.01, especially 4wt% is arrived for 0.1, more particularly 0.2 arrives 3wt%, the total weight based on solid.It include quencher with relatively small amount, such as 0.03 Dao 5wt% based on total weight of solids.Other additives with less equal than 30wt% amount exist, particular less than or wait In 20%, or more preferably less than or equal to 10%, it is based on total weight of solids.It is understood that the solid includes PAG, gathers Close object, light alkali propellant, quencher, surfactant and optional additive.The total of the photo-corrosion-resisting agent composition consolidates Body content can arrive 45wt% for 0.5 to 50wt%, especially 1, and more particularly 2 arrive 40wt%, further preferably 5 arrive 35wt%, are based on The total weight of solid and solvent.It is understood that the solid includes PAG, polymer, light alkali propellant, quencher, surface Activating agent and optional additive are free of solvent.
Photoresist including PAG disclosed herein can be used for providing the layer including photoresist, when consistent Under the conditions of when being exposed to EUV radiation, the concentration for generating volatile degradation products is lower than to be generated containing the layer for comparing photoresist Amount, it is described relatively photoresist include light acid propellant shown in formula (I), wherein G be triphenylsulfonium cation.Opposite Degassing can be determined by such as residual gas analysis (RGA) or film contraction technology.
The substrate of coating can be formed by the photoresist containing PAG.Such coating substrate include: (a) on the surface thereof With one or more layers substrate to be imaged；It (b) include the photoresist containing PAG on one or more layers to be imaged Composition layer.
Substrate can be arbitrary dimension or shape, and preferably those are for photoetching lithographic plate art, such as silicon, silica, insulation Silicon (SOI) on substrate, strained silicon, GaAs, the substrate of coating include coating silicon nitride, silicon oxynitride, titanium nitride, tantalum nitride Substrate, Ultra Thin Gate Oxide such as hafnium oxide, metal or metal coat substrate are including the use of titanium, tantalum, copper, aluminium, tungsten and its alloy The substrate of coating, and combinations thereof.Preferably, the surface of this paper substrate includes critical dimension to be imaged, including such as one layer or Critical dimension in multi-layer gate grade layer or other semiconductors manufactures in substrate used.These substrates preferably include silicon, SOI, answer Become silicon and other such materials, is formed as Circular wafer, the size having such as 200mm, 300mm or larger size, or use In other sizes of wafer manufacture manufacture.
In addition, the forming method of electronic equipment includes (a) for the coating of the photo-corrosion-resisting agent composition including PAG being applied to On the surface of substrate；(b) make photo-corrosion-resisting agent composition layer Imagewise exposure in exciting radiation；(c) and make exposure light Cause resist layer development to provide camegraph.
Application can be completed in any suitable manner, including spin coating, spraying, dip-coating, scraping blade etc..Apply photoresist layer It is completed preferably by coating track by photoresist in spin coating solvents, wherein photoresist distribution is on spin coating chip. During difference, chip can be rotated by being up to the speed of 4,000rpm, preferably from about 500 to 3,000rpm, more preferably 1,000 arrive 2,500rpm.Coated wafer rotation removes solvent, and bakes usually on backing (hot plate) and further remove Residual solvent simultaneously removes free volume (free volume) from film.
Image conversion exposure is carried out using exposure tool such as stepper, wherein the film is illuminated by photomask, thus Carry out image conversion exposure.It is preferred that the method generates activation spoke using advanced exposure tool in the case where that can obtain high-resolution wavelength It penetrates, including extreme ultraviolet (EUV) or electron beam irradiation.It is understood that the exposure using activating radiation is decomposed in exposure area PAG and generate acid and decomposition by-products, and acid then influences in polymer that (deprotection of acid-labile group generates chemical change Alkali solubility group, or optionally, catalytic crosslinking reacts in exposure area).The resolution ratio of these exposure tools is less than 30nm.
Then with the layer of suitable developer processing exposure come the photoresist layer for exposure of developing, the developer can The exposed portion (when photoresist is positivity) of film is selectively removed or except the unexposed portion of striping (works as photoresist When for negativity).Preferably, photoresist is positivity, is based on the polymer with acid-sensitive (can be deprotected) group, and described Developer is preferably the tetraalkylammonium hydroxide solution of non-metallic ion, such as the tetraalkylammonium hydroxide aqueous solution of 0.26N.Aobvious Movie queen forms image.
When in one or more imaging process, the photoresist can be used for preparing electronics and optoelectronic device such as Memory device, processor chips (CPU), graphic chips and similar other equipment.
The present invention further will be illustrated by the following examples.All compounds used are commercially available herein, in addition to What following techniques provided.Divided using INOVA 500NMR (is operated) in 500MHz for proton in OMNI-PROBE from Varian Photometry or GEMINI 300NMR spectrometer (operating for fluorine in 282MHz), determine structure feature by nuclear-magnetism (NMR) spectrogram. If all reagents are all commercially available without other instructions.The PAG of comparing embodiment, triphenylsulfonium 1,1,2,2,3,3,4,4, Nine fluorine butane -1- sulfonate (TPS-PFBus) of 4- and bis- (4- 2-methyl-2-phenylpropane base) iodineNine fluorine butane of 1,1,2,2,3,3,4,4,4-- 1- sulfonate
(DTBPI-PFBus) it is commercially available from Toyo Gosei Co.Ltd.
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