JP2015113292A - Stable acid amplifier - Google Patents

Abstract

An acid amplifier system is provided that can be used in photolithography, in particular for use in extreme UV (13.5 nm) or electron beam lithography.
A sulfonic acid precursor compound represented by formula I or II, a photoresist composition for acid amplification comprising the compound and a photolithographic polymer, a photoresist substrate using the photoresist composition, and a method for producing the same A method of performing photolithography.

[Selection figure] None

Description

  The present invention relates to compositions and methods for acid amplification in photoresists and other related applications.

  Photolithography or optical lithography is a method used in semiconductor device manufacturing that, among other things, transfers a pattern from a photomask (sometimes referred to as a reticle) to the surface of a substrate. Such substrates are well known in the art. For example, silicon, silicon dioxide, and aluminum-aluminum oxide microelectronic wafers have been used as substrates. Gallium arsenide, ceramic, quartz and copper substrates are also known. The substrate often includes a metal coating.

  Photolithography generally involves a combination of substrate preparation, photoresist application and soft baking, radiation exposure, development, etching, and various other chemical treatments (eg, application of thinning agents, edge bead removal, etc.). Is repeated on a substrate that is initially flat. In some more recently developed techniques, a hard bake step is performed after exposure and before development.

  A cycle of a typical silicon lithography procedure involves the coating of a photoresist, ie a material that undergoes a chemical transformation when exposed to radiation (though not generally required, visible light, ultraviolet light, electron beam, or ion beam). Beginning with applying to the surface of the substrate and properly drying the photoresist material (this step is often referred to as “soft baking” of the photoresist as it is typically intended to remove residual solvent) . A transparent plate, called a photomask or shadow mask, on which is imprinted the areas that are to be used and impermeable to radiation, is placed between the radiation source and the layer of photoresist. The portion of the photoresist layer that is not covered by the radiation opaque area of the photomask is then exposed to radiation from the radiation source. Development is performed following exposure. A post-exposure bake (PEB) may be performed following the exposure and before the development. Development is a process in which the entire photoresist layer is chemically treated. During development, the exposed and unexposed areas of the photoresist undergo different chemical changes, thereby removing a set of areas and leaving other areas on the substrate. After development, regions of the upper layer of the substrate that are not covered as a result of the development step are etched away. Finally, the remaining photoresist is removed by an etching or stripping process, leaving an exposed substrate. If a “positive” photoresist is used, the areas of the photomask that are not transparent to radiation remain after development (and therefore the top layer of the substrate, eg, a layer of conductive metal, remains at the end of the cycle). Corresponds to the region. “Negative” photoresist produces the opposite result, ie, areas exposed to radiation remain after development, and masked areas not exposed to radiation are removed after development.

  The need to create physically smaller circuits is steadily increasing over time, and in particular, it is necessary to use shorter and shorter wavelengths of light to enable the formation of these smaller circuits. . This in turn requires a change in the material used as the photoresist, since it is useful as a photoresist, so the material preferably does not absorb the light at the wavelength used. For example, phenolic materials commonly used in photolithography using light with a wavelength of 248 nm are not generally suitable for use as photoresists for 193 nm light, although these phenolic materials tend to absorb 193 nm light. Because there is.

  Currently, it is desirable to use light in the extreme ultraviolet range (13.5 nm or shorter) for photolithography of circuits having line widths of 32-20 nm. Many of the materials that would be suitable for use as positive photoresists in this range include polymers that contain protected groups of acidic groups, such as tert-derived from polyhydroxystyrene or t-butyl acrylate polymers. It is a butoxycarbonyl (t-BOC) protected polymer. Exposure of the masked photoresist to radiation followed by optional post-exposure bake following a “soft bake” of the photoresist results in deprotection of the polymer in areas not covered by the radiation-proof portion of the mask. And thus making these areas susceptible to attack by bases, allowing these areas to be removed during the development stage. In order to achieve this result, it has been proposed to use “chemically amplified” photoresists. The idea is that a positive photoresist polymer after irradiation by including in the photoresist an acid precursor (sometimes called a “photoacid generator” or “PAG”) that is activated by thermally stable photolysis. An acid capable of deprotecting the irradiated portion is generated to make the portion susceptible to base attack.

  In a variation on chemical amplification technology, in the resist composition, a photoacid generator and (a) stable to photolysis and (b) thermally stable in the absence of acid but in the presence of acid. The inclusion of thermally active acid precursors (sometimes referred to as “acid amplifiers”) has been proposed. In such systems, during radiation exposure, the PAG generates acid, which then acts as a catalyst during post exposure bake to activate the acid amplifying agent. Such systems are sometimes referred to in the literature as “acid-amplifier” systems, which catalyze the second acid precursor during post-exposure baking of the acid produced by photolysis during the radiation exposure. This is because it produces an effective number of acid molecules greater than the number of photons absorbed, thus effectively “amplifying” the effect of exposure and amplifying the amount of acid present.

  Similarly, the use of PAGs and acid amplifiers in negative resists has been proposed. In these cases, the acid produced usually changes the polarity or hydrophilicity / hydrophobicity in the exposed areas of the resist by crosslinking or catalyzing the resist in the exposed areas. Thus, the solubility of the resist region exposed to the radiation in the developing solvent is reduced.

Among the difficulties encountered in attempting to implement a chemically amplified photoresist system, “gas evolution” is the process whereby gas is generated as a result of acid formation and the resist film is removed while the wafer is still in the exposure machine. A process that leads to volatile compounds that may leave. Gas evolution may occur under vacuum or under ambient conditions as used in extreme ultraviolet (EUV) lithography. Gas generation is a problem because small molecules may accumulate on the optical elements (lenses or mirrors) of the exposure machine and cause performance degradation. In addition, there is a trade-off between resolution, line width roughness and sensitivity. Resist resolution is generally characterized as the smallest feature that the resist can print. Line width roughness is a statistical variation in line width. Sensitivity is the amount of radioactivity required to print a particular feature on a resist and is usually expressed in units of mJ / cm ² . Further, so far, protected resins that exhibit the required light stability, thermal stability in the absence of acid, and ability to generate thermal acid in the presence of acid, and are used in photolithography. It has been difficult to find acid precursors that generate sufficiently strong acids to deprotect.

  Thus, several acid amplifier systems have been proposed for use in photolithography using 248 nm light, but can be used in photolithography, especially in extreme UV (13.5 nm) or electron beam lithography. There remains a need for an acid amplifier system for use.

  Acid amplifiers (AAs) are subdivided into the following components: triggers, bodies and acid precursors. A trigger is an acid sensitive group that, when activated under acid, allows the compound to decompose and release the acid.

AAs can be classified as Generation 1 (Generation-1), Generation 2, and Generation 3 based on the acid strength they generate and their thermal stability. Generation 1 AAs generates weak non-fluorinated acids, such as toluene sulfonic acid. Generation 2AAs generates moderately strong fluorinated sulfonic acids, such as p- (trifluoromethyl) -benzenesulfonic acid. Generation 3 AAs generate strong fluorinated sulfonic acids, such as triflic acid, and the AAs are thermally stable in the absence of catalytic acid. Acid amplification by further modifying the trigger mechanism by providing two ethers on the same carbon atom, or by a ketal based trigger, with a slightly higher activity at moderate temperatures (90-130 ° C) An agent can also be produced. These are called Generation 4AAs. Examples of four generations are:
It is as follows.

Generation 2 triggers conventionally consist of acid-sensitive leaving groups. After acidification, the group is protonated to erase the compound and regenerate the original acid. The product of elimination produces an olefin, which activates the acid precursor and eliminates it as well. This results in the formation of a second acid and the following:
As shown in FIG. 4, the acid signal is amplified.

  Currently, most acid amplification agents have a trigger that is a leaving group. The acid activates the trigger; the trigger then desorbs to form a double bond. Since the double bond is allylic to the acid, the compound is pyrolyzed to produce the acid.

  Generation 2 trigger type disassembly is energetically advantageous in two respects. EUV photoresists use very strong acids (pKa˜−10). Since these triggers are usually alcohols and ethers (pKa˜−2 to −4), acids are energetically advantageous to protonate these groups. Furthermore, the trigger activation reaction yields two products; an activated body-acid precursor complex and a removed trigger. This increase in product stoichiometry further favors trigger activation as it favors entropy. For these two reasons, the Generation 2 trigger can be activated very easily. However, for EUV photoresists, it has been found that this trigger type is often too sensitive and can result in a sensitive acid amplifier.

In order to improve AA acid strength, AA thermal stability must be increased and degradation must be minimized. Steric hindrance is the best way to reduce nucleophilic attack. Furthermore, generation 2AAs are susceptible to S _N 1 degradation, but a decrease in electron density at the C—O sulfonate bond inhibits the S _N 1 reaction. It has been found that the degradation is controlled by introducing a moiety having a specific characteristic α into the sulfonate ester. Without being bound by theory, this moiety sterically hinders the sulfonate ester from nucleophilic attack and is often highly electron withdrawing, destabilizing carbocation formation. Compounds with this new design are known as stabilized generation 3AAs.

  The reactivity of these compounds can be further modified by changing the trigger mechanism. For example, generation 4AAs can be generated by creating a ketal based (or thioketal based) trigger. These ketal-triggered acid amplifying agents can then be coupled to functional groups that can be introduced into the polymer using free radical polymerization (reaction in refluxing THF for 8-24 hours). The stability of these acid amplifiers also allows other polymer coupling reactions.

In some embodiments, the sulfonic acid precursor in the photoresist composition has the formula (I):
{In the above formula,
G ¹ is —N ⁺ (CH ₃ ) ₃ , — (CH ₂ ) —N ⁺ (CH ₃ ) ₃ , — (CH ₂ ) —NO ₂ , —CH ₂ (CN), —CH (CN) ₂ , _{- (CH 2) 0-1 SO 2} (C 1 -C 8) hydrocarbon _{group, -C 6 F 5, -Si (} CH 3) 3, halogen atom, _-C i _{H j} (halogen _{atom) k,} and during C _s H _t (halogen _atoms) u -E [wherein, i is 1 to 2, j is 0 to 3, k is 1-5, and the sum of j and k is an 2i + 1 And s is 1-2, t is 0-2, u is 1-4, and the sum of t and u is 2s;
E is, - _(C 1 -C ₆₎ alkyl group, an aryl _{group, (C} 1 -C ₆₎ haloalkyl group, a haloaryl group, haloaryl _(C 1 -C ₂₎ alkyl group, and aryl _(C 1 _-C 2) Selected from alkyl groups;
G ² is selected from a hydrogen atom, —CF ₃ , —N ⁺ (CH ₃ ) ₃ , a halogen atom, and a (C ₁ -C ₁₀ ) hydrocarbon group;
AA is the following part:
a)
[In the above formula,
M is —O—, —S—, or —NR ⁹⁰ —;
R ¹⁰ is a (C ₁ -C ₈ ) saturated hydrocarbon group; a (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group, or a nitro group; (C ₁ -C ₈ ) a silaalkane group ; -O- _(C 1 -C ₈₎ saturated hydrocarbon group; a halogen atom, a cyano group, or a -O- substituted with nitro group _(C 1 -C ₈₎ saturated hydrocarbon group; -S- _{(C 1} -C ₈₎ saturated hydrocarbon group; a halogen atom, a cyano group, or a substituted -S- (C 1 _{-C 8)} saturated hydrocarbon group a nitro group; and optionally, a phenyl group which may have been substituted Selected from;
R ²⁰ is selected from H, a (C ₁ -C ₆ ) hydrocarbon group and a nitro group, or a (C ₁ -C ₆ ) hydrocarbon group substituted with a cyano group, or R ¹⁰ and R ²⁰ Together with the carbon atom to which they are attached form a 3-8 membered ring;
R ⁴⁰ is H, (C ₁ -C ₆ ) alkyl group, —C (═O) (C ₁ -C ₆ ) alkyl group, —C (═O) (C ₁ -C ₆ ) alkenyl group, —C (═O) (C ₁ -C ₆ ) haloalkyl group, benzyl group, substituted benzyl group, —C (═O) phenyl group, —C (═O) substituted phenyl group, —SO ₂ phenyl group, —SO ₂ ( Selected from a substituted) phenyl group; or when M is O or S, R ¹⁰ and R ⁴⁰ are optionally one or more (C ₁ -C ₆ ) hydrocarbons. Can form a 4-8 membered ring that may be substituted with groups;
R ⁵⁰ is H, (C ₁ -C ₆ ) hydrocarbon group, nitro group, cyano group, nitro group, (C ₁ -C ₆ ) hydrocarbon group substituted with cyano group, and (C ₁ -C ₆ ) selected from silaalkane groups, or R ¹⁰ and R ⁵⁰ together with the carbon atom to which they are attached form a (C ₃ -C ₈ ) hydrocarbon ring; or When O or S, R ²⁰ and R ⁵⁰ together form a 3- to 8-membered ring that is optionally substituted with one or more (C ₁ -C ₆ ) hydrocarbon groups. It is possible;
R ⁹⁰ is selected from H, a (C ₁ -C ₆ ) alkyl group, a —C (═O) (C ₁ -C ₆ ) alkyl group, and a phenyl group, or R ⁴⁰ and R ⁹⁰ are They can be taken together with the attached nitrogen atom to form a nitrogen heterocycle, provided that one of R ⁴⁰ and R ⁹⁰ must be an acyl group and R ⁴⁰ and R ⁹⁰ are When they together with the bound nitrogen atom form a heterocycle, the heterocycle shall contain one or two α-oxo substituents]; and b)
[In the above formula,
R ^{w, R x} and ^{R y} are independently hydrogen atoms in each case _is selected from (C 1 _{-C 10)} hydrocarbon group, and _(C 1 -C ₈₎ Shiraarukan group;
R ¹⁰⁰ is selected from a hydrogen atom and a (C ₁ -C ₂₀ ) hydrocarbon group; or any ^two of R ¹⁰⁰ , R ^w , R ^x , R ^y and G ² are Together with the bonded carbon atoms, forms a (C ₅ -C ₈ ) hydrocarbon ring that can be substituted with a (C ₁ -C ₈ ) hydrocarbon group, provided that C = C Double bonds are not included in the phenyl ring]
Or c) G ¹ and AA together with the carbon atom to which they are attached are non-aromatic 5 or 6 membered rings D:
[In the above formula,
R ^g is independently in each case a hydrogen atom, —M—R ⁴⁰ , (C ₁ -C ₁₀ ) hydrocarbon group, hydroxyl group, and R ^h CH ₂ COO— (where R ^h is halogen) Represents one or two substituents selected from atoms, hydroxyl groups, polymers, and oligomers; and G ³ represents —N ⁺ (CH ₃ ) ₂ , — (CH) —NO ₂ , — _{CH (CN), - C (} CN) 2, -Si (CH 3) 2 -, - C i H j in (halogen _{atom) k,} and _C s _{H t} (halogen _atoms) u -E (wherein, i is 1-2, j is 0-3, k is 1-5, and the sum of j and k is 2i; and s is 1-2 and t is 0-2 , U is 1-4, and the sum of t and u is 2s-1 (2s minus 1)); To ^{R A} and ^{R B} are each independently a hydrogen _{atom, (C} 1 -C ₆₎ may be selected from alkyl and benzyl group,]
AB is selected from F and CF ₃ ;
AC represents —C (═O) NR ^AC —, —C (═O) O—, —CH ₂ O—, —CH ₂ OC (═O) —, and —CH ₂ OC (═O) NR ^AC —. Wherein R ^AC is selected from a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, and a phenyl group;
AD is a direct _{^{bond, - (CR AD R AD)}} m (O) -, - (CR AD R AD) m (O) n (C = O) -, - (CR AD R AD) m (NR AD) _{n (C = O) p -} , - AE (O) n (C = O) p -, and _{^{-AE (NR AD) n (C}} = O) p - is selected from;
m is 0, 1, 2, 3, or 4;
n is 0 or 1;
p is 0 or 1;
R ^AD can be independently selected from a hydrogen atom and a (C ₁ -C ₆ ) alkyl group;
AE is
Is;
R ⁷² was independently selected in each case from a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, a — (C ₁ -C ₄ ) haloalkyl group, —NO ₂ , F, Br, and Cl. Represents 1 to 4 substituents;
AF is the next part:
_{a) -C (= CH 2)} AG;
b) -C _a H _b F _{c wherein} a is 1-15, b is 0-30, C is 1-31, and the sum of b and c is 2a + 1;
c)-(R ^d ) or -C _A H _B (R ^d ) _{D wherein} A is selected from 1, 2, 3, and 4; B is selected from an integer between 0 and 1-9; D is selected from 1, 2 and 3 and the sum of B and D is 2A + 1; R ^d is in each case selected from a hydrogen atom and a (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group The (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group can optionally be substituted with one or more substituents selected from R ⁶¹ and R ⁷¹ ; and At least one example of R ^d is a (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group];
d)
e)
Selected from
AG is selected from H, F, CH ₃ , and CF ₃ in each case;
R ⁶¹ is H, —OH, —CF ₃ , — (C ₁ -C ₄ ) alkyl group, —OCH ₃ , —C (═O) OR ^AD , —OC (═O) R ^AD , —C (= O) R ^AD , cyano group, —NO ₂ , F, Cl, Br, —CH ₂ Br, —CH═CH ₂ , —OCH ₂ CH ₂ Br, —OC═OCH═CH ₂ , and —OC═OCCH ₃ = Selected from CH ₂ ;
R ⁷¹ is, in each case, H, —CF ₃ , —OH, —OCH ₃ , —C═O (oxo), — (C ₁ -C ₄ ) alkyl, —NO ₂ , F, Br, Cl , -C _i H _j (halogen atom) _k and C _s H _t (halogen atom) _u -E represent 1 to 4 substituents independently selected, wherein i is 1 to 2; j is 0-3, k is 1-5, and the sum of j and k is 2i + 1; and s is 1-2, t is 0-2, u is 1-4 And the sum of t and u is 2 s; and E is a — (C ₁ -C ₆ ) alkyl group, an aryl group, a (C ₁ -C ₆ ) haloalkyl group, a haloaryl group, a haloaryl (C ₁ — C ₂₎ is selected from an alkyl group, and aryl _(C 1 -C ₂₎ alkyl group. }
It is a compound represented by these.

In some embodiments, the present invention provides compounds of formula II:
{In the formula, G ¹ represents -N ⁺ (CH ₃ ) ₃ ,-(CH ₂ ) -N ⁺ (CH ₃ ) ₃ ,-(CH ₂ ) -NO ₂ ,-(CH ₂ ) (CN),-( CH) (CN) ₂ , — (CH ₂ ) _0-1 SO ₂ (C ₁ -C ₈ ) hydrocarbon group, —C ₆ F ₅ , —Si (CH ₃ ) ₃ , halogen atom, —C _i H _j (Halogen atom) _k and -C _s H _t (halogen atom) _u -E, wherein i is 1-2, j is 0-3, k is 1-5, And the sum of j and k is 2i + 1; and s is 1-2, t is 0-2, u is 1-4, and the sum of t and u is 2s; E is , - _(C 1 -C ₆₎ alkyl group, an aryl _{group, (C} 1 -C ₆₎ haloalkyl group, a haloaryl group, haloaryl _(C 1 -C ₂₎ alkyl group, Fine aryl _(C 1 -C ₂₎ is selected from an alkyl group;
G ² is selected from a hydrogen atom, —CF ₃ , —N ⁺ (CH ₃ ) ₃ , a halogen atom and a (C ₁ -C ₁₀ ) hydrocarbon group;
AA is the following part:
a)
Wherein M is —O—, —S—, or —NR ⁹⁰ —;
R ¹⁰ is a (C ₁ -C ₈ ) saturated hydrocarbon group; a (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group, or a nitro group; (C ₁ -C ₈ ) a silaalkane group ; -O- _(C 1 -C ₈₎ saturated hydrocarbon group; a halogen atom, a cyano group, or -O- substituted with nitro group _(C 1 -C ₈₎ saturated hydrocarbon group; -S- _{(C 1} -C ₈₎ saturated hydrocarbon group; a halogen atom, substituted with a cyano group or a nitro group -S- (C 1 _{-C 8)} saturated hydrocarbon group; and, optionally, a phenyl group which may be substituted And R ²⁰ is selected from H, (C ₁ -C ₆ ) hydrocarbon group, and nitro group, cyano group or substituted (C ₁ -C ₆ ) hydrocarbon group, or Together with the bonded carbon, R ¹⁰ and R ²⁰ are 3-8 membered rings Forming;
R ^40a is H, (C ₁ -C ₆ ) alkyl group, —C (═O) (C ₁ -C ₆ ) alkyl group, —C (═O) (C ₁ -C ₆ ) alkenyl group, —C (═O) (C ₁ -C ₆ ) haloalkyl group, benzyl group, substituted benzyl group, —C (═O) phenyl group, substituted —C (═O) phenyl group, —SO ₂ phenyl group, —SO ₂ (substituted) phenyl group and Q; or when M is O or S, both R ¹⁰ and R ^40a are optionally one or more (C ₁ -C ₆ ) Can form a 4-8 membered ring which may be substituted with a hydrocarbon group;
R ⁵⁰ represents H, a (C ₁ -C ₆ ) hydrocarbon group, a nitro group, a cyano group, a cyano group, a (C ₁ -C ₆ ) hydrocarbon group substituted with a nitro group, and (C ₁ -C _6). ) Selected from silaalkane groups, or together with the carbon to which they are attached, R ¹⁰ and R ^{50 form} a (C ₃ -C ₈ ) hydrocarbon ring; or M is O or When S, R ²⁰ and R ⁵⁰ can together form a 3- to 8-membered ring that may be optionally substituted with one or more (C ₁ -C ₆ ) hydrocarbon groups. ;
R ⁹⁰ is selected from H, (C ₁ -C ₆ ) alkyl group, —C (═O) (C ₁ -C ₆ ) alkyl group, and phenyl group, or together with the nitrogen to which they are attached. R ^40a and R ⁹⁰ can form a nitrogen heterocycle and together with the nitrogen to which they are attached provided that one of R ^40a and R ⁹⁰ must be an acyl group When R ^40a and R ⁹⁰ form a heterocycle, the heterocycle must contain 1 or 2 α-oxo substituents]; and b)
[Wherein R ^W , R ^X and R ^y are each independently selected from a hydrogen atom, a (C ₁ -C ₁₀ ) hydrocarbon group and a (C ₁ -C ₈ ) silaalkane group;
R ¹⁰⁰ is selected from a hydrogen atom and a (C ₁ -C ₂₀ ) hydrocarbon group; or any ^two of R ¹⁰⁰ , R ^W , R ^X , R ^y and G ² are the carbons to which they are attached. Together with (C ₁ -C ₈ ) to form a (C ₅ -C ₈ ) hydrocarbon ring which may be substituted with a hydrocarbon group, provided that the C═C double bond is within the phenyl ring Or c) G ¹ and AA together with the carbon to which they are attached are non-aromatic 5 or 6 membered rings D:
[Wherein R ^g is 1 or independently selected from a hydrogen atom, —M—R ^40a , (C ₁ -C ₁₀ ) hydrocarbon group, hydroxyl group and R ^h CH ₂ COO— in each case. 2 wherein R ^h is selected from halogen atoms, hydroxyl groups, polymers, and oligomers; and G ³ is —N ⁺ (CH ₃ ) ₂ , — (CH) —NO _{2, -CH (CN), -} C (CN) 2, -Si (CH 3) 2 -, - C i H j ( _{halogen) k,} and is selected from _-C s _{H t (halogen)} u -E, Where i is 1-2, j is 0-3, k is 1-5, and the sum of j and k is 2i; and s is 1-2 and t is 0 ~ 2, u is 1-4, and the sum of t and u is 2s-1; and R ^A and And R ^B can be independently selected from a hydrogen atom, a (C ₁ -C ₆ ) alkyl group and a benzyl group];
Can form
AB is selected from F and CF ₃ ;
AC represents —C (═O) NR ^AC —, —C (═O) O—, —CH ₂ O—, —CH ₂ OC (═O) —, and —CH ₂ OC (═O) NR ^AC —. Wherein R ^AC is selected from a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, and a phenyl group;
AD is a direct _{^{bond, - (CR AD R AD)}} m (O) -, - (CR AD R AD) m (O) n (C = O) -, - (CR AD R AD) m (NR AD) _{n (C = O) p -} , - AE (O) n (C = O) p -, and _{^{-AE (NR AD) n (C}} = O) p - is selected from;
m is 0, 1, 2, 3 or 4;
n is 0 or 1;
p is 0 or 1;
R ^AD can be independently selected from a hydrogen atom and a (C ₁ -C ₆ ) alkyl group;
AE is
Is;
R ⁷² was independently selected in each case from a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, a — (C ₁ -C ₄ ) haloalkyl group, —NO ₂ , F, Br, and Cl. Represents 1 to 4 substituents;
AF ^a is the following part:
_{a) -C (= CH 2)} AG;
b) -C (AG) (Q ) CH 2 Q;
c) -C _a H _b F _c [wherein a is 1-15, b is 0-30, C is 1-31, and the sum of b and c is 2a + 1];
d)-(R ^d ) or -C _A H _B (R ^d ) _{D wherein} A is selected from 1, 2, 3, and 4, B is selected from an integer between 0 and 1-9; D is selected from 1, 2 and 3 and the sum of B and D is 2A + 1; R ^d is in each case selected from hydrogen and a (C ₃ -C ₁₂ ) alicyclic hydrocarbon group, The (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group can be optionally substituted with one or more substituents selected from R ^61a and R ⁷¹ ; and R ^{d in} the formula At least one example of is an optionally substituted (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group];
e)
f)
Selected from
AG is selected from H, F, CH ₃ , and CF ₃ in each case;
R ^61a is H, —OH, —CF ₃ , — (C ₁ -C ₄ ) alkyl group, —OCH ₃ , —C (═O) OR ^AD , —OC (═O) R ^AD , —C (= O) R ^AD , cyano group, —NO ₂ , F, Cl, Br, —CH ₂ Br, —CH═CH ₂ , —OCH ₂ CH ₂ Br, —Q, —CH ₂ —Q, —O—Q, _{-OCH 2 CH 2 -Q, -OCH 2} CH 2 O-Q, -CH (Q) CH 2 -Q, -OC = OCH = CH 2, -OC = OCCH 3 = CH 2, -OC = OCHQCH 2 Q And —OC═OCCH ₃ QCH ₂ Q;
R ⁷¹ is, in each case, H, —CF ₃ , —OH, —OCH ₃ , —C═O (oxo), — (C ₁ -C ₄ ) alkyl, —NO ₂ , F, Br, Cl , -C _i H _j (halogen atom) _k and -C _s H _t (halogen) _u -E independently represent 1 to 4 substituents, wherein i is 1 to 2; j is 0-3, k is 1-5, and the sum of j and k is 2i + 1; and s is 1-2, t is 0-2, u is 1-4 And the sum of t and u is 2s;
E is, - _(C 1 -C ₆₎ alkyl group, an aryl _{group, (C} 1 -C ₆₎ haloalkyl group, a haloaryl group, haloaryl _(C 1 -C ₂₎ alkyl group, and aryl _(C 1 _-C 2) Selected from alkyl groups; and Q is a polymer or oligomer;
Wherein at least one of the substituents of the compound shall be Q or shall contain Q}
It relates to a compound represented by

  All compounds that fall within the above superclasses and their subclasses are useful for photolithography. In examination, it may be recognized that the compounds encompassed by the claims cannot be patented to the inventor of the present application. In this case, it is a product of the patent application procedure that the applicant subsequently excludes the type from the scope described in the claims, and the concept of the inventors or the description of the invention is not reflected. The present invention encompasses all three members of the above three categories that are not yet owned by the public. The present invention also encompasses the use of a wider variety of compounds in photoresists.

The acid amplifying agents disclosed herein are largely, if not all, novel, and thus in some embodiments of the invention the molecules themselves as well as methods for their production are provided. In this aspect, the invention provides the following:
[The definitions in the formula are shown above]
It relates to a compound having the formula represented by: The compounds disclosed by international patent application PCT / US2012 / 030850 filed on March 28, 2012 are not expressly disclaimed as not covered by this disclosure.

  In some embodiments, the present invention relates to a photolithographic composition comprising a photolithographic polymer and a compound represented herein.

  In some embodiments, the present invention relates to a photoresist composition comprising a photoresist polymer and a compound represented herein. In some embodiments, the photoresist composition is suitable for producing a positive photoresist. In some embodiments, the photoresist composition is suitable for producing a negative photoresist. In some embodiments, the photoresist composition is suitable for making a photoresist using 248 nm, 193 nm, 13.5 nm light, or using electron or ion beam radiation.

  According to some embodiments, the present invention relates to a method of manufacturing photolithography, comprising coating a substrate with the aforementioned photoresist composition.

  In some embodiments, the present invention performs photolithography on a substrate comprising providing the substrate, coating the substrate with the above-described photoresist composition, and irradiating the coated substrate through a photomask. On how to do. In some embodiments, the irradiation is performed using electromagnetic radiation with a wavelength of 248 nm, 193 nm, 13.5 nm, or radiation from an electron or ion beam.

  In some embodiments of the present invention, a substrate covering a photoresist composition according to the present invention is also provided. In some embodiments, the substrate includes a conductive film, an insulating layer, and a semiconductor layer coated with a photoresist composition thereon.

  According to an embodiment of the present invention, there is provided an etching method for performing photolithography on a substrate, comprising: (a) supplying the substrate; and (b) applying the substrate with the photoresist composition according to the embodiment of the present invention. An etching method is also provided that includes coating and (c) irradiating the coated substrate through a photomask.

  In some embodiments, the coating method includes applying a photoresist composition to the substrate and baking the photoresist composition applied on the substrate.

  In some embodiments, the irradiation is performed using radiation of sufficient energy and sufficient time to generate an acid on the portion of the photoresist composition coated on the substrate that is exposed to the radiation. Is done. For example, the irradiation is performed using electromagnetic radiation with a wavelength of 248 nm, 193 nm, 13.5 nm, or radiation from an electron beam or ion beam.

  In some embodiments, the method further comprises baking the coated substrate after irradiation but before development. In some embodiments, baking is performed at a temperature and for a time sufficient for the sulfonic acid precursor in the photoresist coating to generate sulfonic acid.

It is a figure which shows the rotational speed of coating of each of four resist films, ie, three acid amplification agents, and one control.

FIG. 6 shows the lithography results of four resists at three different post-exposure baking (PEB) temperatures.

《Detailed explanation》
Substituents are generally defined as introduced and retain their definition throughout the specification and in all the independent claims.

In some embodiments, the invention provides a compound of formula (I):
It relates to a compound represented by

In some embodiments, the present invention provides the following formula (II):
It relates to a compound represented by

In some embodiments, AA is
It is. In other embodiments, AA is
It is. In still other embodiments, AA is
It is. In yet other embodiments, G ¹ and AA are taken together with the carbon atom to which they are attached to form a non-aromatic 5- or 6-membered ring D:
Can be formed.

  In some embodiments, D is a saturated 5 or 6 membered ring. In other embodiments, D is an unsaturated 5- or 6-membered ring.

In some embodiments, G ¹ is —N ⁺ (CH ₃ ) ₃ . In some embodiments, G ¹ is — (CH ₂ ) —N ⁺ (CH ₃ ) ₃ . In other embodiments, G ¹ is — (CH ₂ ) —NO ₂ . In other embodiments, G ¹ is C ₆ F ₅ . In other embodiments, G ¹ is —CH ₂ (CN) or —CH (CN) ₂ . In some embodiments, G ¹ is a — (CH ₂ ) _0-1 SO ₂ (C ₁ -C ₈ ) hydrocarbon group. For example, in some embodiments, G ¹ can be a —SO ₂ (CH ₃ ) or — (CH ₂ ) SO ₂ -benzyl group. In yet other embodiments, G ¹ is —Si (CH ₃ ) ₃ . In still other embodiments, G ¹ is a halogen atom. In some embodiments, G ¹ is —C _i H _j (halogen atom) _k , wherein i is 1-2, j is 0-3, k is 1-5, and The sum of j and k is 2i + 1). As an example, in these embodiments, G ¹ can be —CH ₂ F, —CF ₂ H, or —CF ₃ . In some embodiments, G ¹ is C _s H _t (halogen atom) _u -E, wherein s is 1-2, t is 0-2, u is 1-4, And the sum of t and u is 2s). As an example, in these embodiments, G ¹ can be C ₂ H ₂ F ₂ -E.

In some embodiments, E is - _(C 1 -C ₆₎ alkyl or _(C 1 -C ₆₎ haloalkyl group. In other embodiments, E is an aryl group or a haloaryl group. In still other embodiments, E is a haloaryl (C ₁ -C ₂ ) alkyl group or an aryl (C ₁ -C ₂ ) alkyl group.

In some embodiments, G ² is a hydrogen atom. In some embodiments, G ² is —CF ₃ . In some embodiments, G ² is —N ⁺ (CH ₃ ) ₃ . In some embodiments, G ² is a halogen atom. In some embodiments, G ² is a (, C ₁ -C ₁₀ ) hydrocarbon group. For example, in some embodiments, G ² is a saturated or unsaturated group that may be linked by a (C ₁ -C ₁₀ ) alkyl group, a (C ₂ -C ₁₀ ) alkenyl group, or optionally a methylene group. cyclic saturated _(C 4 -C ₈₎ can be a hydrocarbon group.

In certain embodiments, M is an oxygen atom. In certain embodiments, M is —NR ⁹⁰ —. In certain embodiments, M is a sulfur atom.

In some embodiments, R ⁹⁰ is a hydrogen atom. In some embodiments, R ⁹⁰ is a (C ₁ -C ₆ ) alkyl group. In some embodiments, R ⁹⁰ is a —C (═O) (C ₁ -C ₆ ) alkyl group. In some embodiments, R ⁹⁰ is a phenyl group.

In certain embodiments, R ¹⁰ is a (C ₁ -C ₈ ) saturated hydrocarbon group. In certain embodiments, R ¹⁰ is a (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group, or a nitro group. In certain embodiments, R ¹⁰ is a (C ₁ -C ₈ ) silaalkane group. In some embodiments, R ¹⁰ is a —O— (C ₁ -C ₈ ) saturated hydrocarbon group. In some embodiments, R ¹⁰ is a —O— (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group, or a nitro group. In some embodiments, R ¹⁰ is a —S— (C ₁ -C ₈ ) saturated hydrocarbon group. In some embodiments, R ¹⁰ is a —S— (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group, or a nitro group. In certain embodiments, R ¹⁰ is an optionally substituted phenyl group. In certain embodiments, R ¹⁰ is selected from a methyl group, a propenyl group, a propynyl group, a dimethylbutynyl group, a cyclopropyl group, a trimethylsilylmethyl group, a phenyl group, a nitrophenyl group, a nitromethyl group, and a cyanomethyl group.

In some embodiments, R ²⁰ is selected from a hydrogen atom, a (C ₁ -C ₆ ) hydrocarbon group, and a (C ₁ -C ₆ ) hydrocarbon group substituted with a nitro group or a cyano group. In some embodiments, R ²⁰ is a hydrogen atom. In other embodiments, R ²⁰ is a methyl group.

In some embodiments, R ¹⁰ and R ²⁰ together with the carbon atom to which they are attached form a 3-8 membered ring. In some embodiments, R ¹⁰ and R ²⁰ are taken together to form a cyclobutyl ring, a cyclopentyl ring, or a cyclohexyl ring.

In some embodiments, R ⁵⁰ is H, (C ₁ -C ₆ ) hydrocarbon group, nitro group, cyano group, nitro group or (C ₁ -C ₆ ) hydrocarbon group substituted with cyano group, And (C ₁ -C ₆ ) silaalkane groups. In some embodiments, R ⁵⁰ is H. In some embodiments, R ⁵⁰ is NO ₂ . In some embodiments, R ⁵⁰ is CN. In some embodiments, R ⁵⁰ is SiMe ₃ . In some embodiments, R ⁵⁰ is a methyl group. In some embodiments, R ⁵⁰ is a phenyl group.

In some embodiments, R ¹⁰ and R ⁵⁰ together with the carbon atom to which they are attached form a (C ₃ -C ₈ ) hydrocarbon ring. In other embodiments, R ¹⁰ and R ⁵⁰ are taken together to form a cyclopentyl or cyclohexyl ring. In some embodiments, when M is O or S, R ²⁰ and R ⁵⁰ are taken together and optionally substituted with one or more (C ₁ -C ₆ ) hydrocarbon groups. 3-8 membered rings that may be present can be formed.

In some embodiments, R ⁴⁰ is H, (C ₁ -C ₆ ) alkyl, —C (═O) (C ₁ -C ₆ ) alkyl, —C (═O) (C ₁ -C). ₆₎ alkenyl group, -C (= _{O) (C} 1 -C ₆₎ haloalkyl group, a benzyl group, substituted benzyl group, -C (= O) phenyl group, -C (= O) substituted phenyl group, -SO ₂ It is selected from a phenyl group and a —SO ₂ (substituted) phenyl group. In some embodiments, R ⁴⁰ is H, methyl, ethyl, isopropyl, t-butyl, benzyl, acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4- (Trifluoromethyl) benzoyl group, 4-nitrobenzoyl group, 4-carboxybenzoyl group, 4-methoxybenzoyl group, benzenesulfonyl group, 4- (trifluoromethyl) benzenesulfonyl group, 4-nitrobenzenesulfonyl group, 4-carboxy It is selected from a benzenesulfonyl group and a 4-methoxybenzenesulfonyl group.

In some embodiments, R ^40a is H, (C ₁ -C ₆ ) alkyl, —C (═O) (C ₁ -C ₆ ) alkyl, —C (═O) (C ₁ -C). ₆₎ alkenyl group, -C (= _{O) (C} 1 -C ₆₎ haloalkyl group, a benzyl group, substituted benzyl group, -C (= O) phenyl group, -C (= O) substituted phenyl group, -SO ₂ It is selected from a phenyl group and a —SO ₂ (substituted) phenyl group. In other embodiments, R ^40a can be Q. In some embodiments, R ⁴⁰ is H, methyl, ethyl, isopropyl, t-butyl, benzyl, acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4- ( (Trifluoromethyl) benzoyl group, 4-nitrobenzoyl group, 4-carboxybenzoyl group, 4-methoxybenzoyl group, benzenesulfonyl group, 4- (trifluoromethyl) benzenesulfonyl group, 4-nitrobenzenesulfonyl group, 4-carboxybenzene It is selected from a sulfonyl group and a 4-methoxybenzenesulfonyl group.

In some embodiments, when M is O or S, R ¹⁰ and R ⁴⁰ or R ¹⁰ and R ^{40a taken} together are optionally _one (C ₁ -C ₆ ) hydrocarbon group or Forms a 4-8 membered ring that may be substituted with 2 or more. In some embodiments, the ring formed by R ¹⁰ and R ⁴⁰ or R ¹⁰ and R ^40a is
It is. In other embodiments, the ring formed by R ¹⁰ and R ⁴⁰ or R ¹⁰ and R ^40a is
It is. In some embodiments, R ⁸⁰ can in each case be a hydrogen atom or one or more (C ₁ -C ₆ ) hydrocarbon groups. For complete clarity, by way of example, R ⁸⁰ can be a methyl group at one position and an ethyl group at another position, or can be a hydrogen atom at all positions, or 2 It can be a methyl group at one position. In some embodiments, R ⁴⁰ and R ⁹⁰ or R ⁴⁰ and R ^90a together with the nitrogen atom to which they are attached form a nitrogen heterocycle containing one or two α-oxo substituents. be able to. In other embodiments, one of R ⁴⁰ and R ⁹⁰ or R ⁴⁰ and R ^90a must be an acyl group.

In some embodiments, M is an oxygen atom and R ⁴⁰ or R ^40a is H, methyl group, ethyl group, isopropyl group, t-butyl group, benzyl group, acetyl group, chloroacetyl group, dichloroacetyl group. , Trichloroacetyl group, benzoyl group, 4- (trifluoromethyl) benzoyl group, 4-nitrobenzoyl group, 4-carboxybenzoyl group, 4-methoxybenzoyl group, benzenesulfonyl group, 4- (trifluoromethyl) benzenesulfonyl group , 4-nitrobenzenesulfonyl group, 4-carboxybenzenesulfonyl group, and 4-methoxybenzenesulfonyl group.

In certain embodiments, M is —NR ⁹⁰ —. In these embodiments, R ⁴⁰ or R ^40a is selected from H, methyl group, ethyl group, isopropyl group, t-butyl group and benzyl group. In some embodiments, R ⁹⁰ can be an acetyl group. In other embodiments, R ⁴⁰ and R ⁹⁰ together with the nitrogen atom to which they are attached form a pyrrolidone, phthalimide, maleimide, or succinimide ring.

In some embodiments, M is a sulfur atom, and R ⁴⁰ or R ^40a is H, methyl group, ethyl group, isopropyl group, t-butyl group, benzyl group, acetyl group, chloroacetyl group, dichloroacetyl group. , A trichloroacetyl group, a benzoyl group, a 4- (trifluoromethyl) benzoyl group, a 4-nitrobenzoyl group, a 4-carboxybenzoyl group, and a 4-methoxybenzoyl group.

In still other embodiments, AA is
It is. In some embodiments, R ^w , R ^x, and R ^y are independently from each other from a hydrogen atom, a (C ₁ -C ₈ ) silaalkane group, and a (C ₁ -C ₁₀ ) hydrocarbon group. Selected. In some embodiments, R ^w , R ^x and R ^y are independently at each occurrence a hydrogen atom, a (C ₁ -C ₁₀ ) alkyl group, a (C ₂ -C ₁₀ ) alkenyl group, and optionally , Selected from saturated or unsaturated cyclic (C ₄ -C ₈ ) hydrocarbon groups which may be linked by a methylene group. In some embodiments, R ^y is a hydrogen atom or a (C ₁ -C ₇ ) hydrocarbon group. In other embodiments, R ^y is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, or a benzyl group. In some embodiments, R ^x is selected from groups that stabilize cations formed on the carbon atom to which R ^x is attached. For example, R ^x can be selected from a phenyl group, an alkene group, an alkyne group, a cyclopropyl group, and —CH ₂ Si (CH ₃ ) ₃ .

In certain embodiments, R ¹⁰⁰ is selected from a hydrogen atom and a (C ₁ -C ₂₀ ) hydrocarbon group. In some embodiments, R ¹⁰⁰ is a saturated or hydrogen atom, a (C ₁ -C ₁₀ ) alkyl group, a (C ₂ -C ₁₀ ) alkenyl group, and optionally a methylene group. It is selected from unsaturated cyclic (C ₄ -C ₈ ) hydrocarbon groups. In some embodiments, R ¹⁰⁰ is selected from an H atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and a benzyl group. In other embodiments, R ¹⁰⁰ is selected from an H atom, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a phenyl group, and a benzyl group.

In some embodiments, any ^two of R ¹⁰⁰ , R ^w , R ^x , R ^y, and G ² are taken together with the carbon atom to which they are attached to form a (C ₁ -C ₈ ) hydrocarbon. (C ₅ -C ₈ ) hydrocarbon rings which can be substituted with groups are formed. In some embodiments, any ^two of R ¹⁰⁰ , R ^w , R ^x , R ^y, and G ² together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl ring. In some embodiments, R ^y and G ² are taken together to form a cyclopentyl or cyclohexyl ring, each of which is optionally substituted with a (C ₁ -C ₈ ) alkyl group. Can do. In other embodiments, R ^x and G ² together form a cyclopentyl or cyclohexyl ring, each of which is optionally substituted with a (C ₁ -C ₈ ) alkyl group. it can.

In some aspects of the invention, the bonds in the substituents around the backbone C═C double bond can be balanced. For example, if R ¹⁰⁰ or R ^w is an aryl group, it may be advantageous that R ^y is also an aryl group. By doing so, isomerization of the C═C double bond can occur without migration from the bond.

In some embodiments, G ¹ and AA are taken together with the carbon atom to which they are attached to form a non-aromatic 5- or 6-membered ring D:
Can be formed. In some embodiments of the invention, D is a saturated 5 or 6 membered ring. In other embodiments, D is an unsaturated 5- or 6-membered ring.

In some embodiments, R ^g is independently in each case a hydrogen atom, —M—R ⁴⁰ , (C ₁ -C ₁₀ ) hydrocarbon group, hydroxyl group, R ^h CH ₂ COO—, and R one substituent selected from ^ha CH ₂ COO—, wherein R ^h is selected from a halogen atom, a hydroxyl group, and R ^ha is selected from a halogen atom, a hydroxyl group, a polymer, and an oligomer, or Represents two. In certain embodiments, R ^g is independently selected from a hydrogen atom and a (C ₁ -C ₁₀ ) hydrocarbon group in each case. In other embodiments, R ^g is selected from a hydrogen atom, a methyl group, and a vinyl group. In some embodiments, R ^g is -M-R ⁴⁰ . In some embodiments, R ^g is -M-R ^40a .

In some embodiments, R ^A is a hydrogen atom. In some embodiments, R ^A is a (C ₁ -C ₆ ) alkyl group. In some embodiments, R ^A is a benzyl group. In some embodiments, R ^B is a hydrogen atom. In some embodiments, R ^B is a (C ₁ -C ₆ ) alkyl group. In some embodiments, R ^B is a benzyl group. In some embodiments, R ^A and R ^B are both hydrogen atoms.

In some embodiments, G ³ is —N ⁺ (CH ₃ ) ₂ , — (CH) —NO ₂ , —CH (CN), —C (CN) ₂ , —Si (CH ₃ ) ₂ — ( CH ₂ ) —, —C _i H _j (halogen atom) _k , and —C _s H _t (halogen atom) _u —E, wherein i is 1 to 2 and j is 0 to 3 , K is 1-5, and the sum of j and k is 2i; and s is 1-2, t is 0-2, u is 1-4, and t And the sum of u is 2s-1. In certain embodiments, G ³ is —N ⁺ (CH ₃ ) ₂ .

In some embodiments, AB is F. In other embodiments, AB is CF ₃ . In some embodiments, the —CF (AB) — moiety can be —CH ₂ — or —CHF—.

In some embodiments, AC is —C (═O) NR ^AC —. In some embodiments, AC is —C (═O) NH. In other embodiments, AC is -C (= O) O-. In still other embodiments, AC is —CH ₂ O—. In some embodiments, AC is —CH ₂ OC (═O) —. In other embodiments, AC is —CH ₂ OC (═O) NR ^AC —.

In some embodiments, R ^AC is a hydrogen atom. In other embodiments, R ^AC is a (C ₁ -C ₆ ) alkyl group. In some embodiments, R ^AC is a phenyl group. In some embodiments, AC is —C (═O) NH.

In some embodiments, AD is a direct bond. In some embodiments, AD is — (CR ^AD R ^AD ) _m (O) —. In some embodiments, AD is — (CR ^{ADR A AD} ) _m (O) _n (C═O) —. In other embodiments, AD is _{^{-, (CR AD R AD)}} 2 (O) (C = O) - is. In other embodiments, AD is —C (═O) —. In some embodiments, AD is — (CH ₂ ) ₂ O—. In some embodiments, AD _{^{is, - (CR AD R AD)}} m (NR AD) n (C = O) p - is. In some embodiments, AD is AE (O) _n (C═O) _p —. In some embodiments, AD is
It is. In yet other embodiments, AD is —AE (NR ^AD ) _n (C═O) _p —.

  In some embodiments, m is 0. In other embodiments, m is 1. In other embodiments, m is 2. In other embodiments, m is 3. In other embodiments, m is 4.

  In some embodiments, n is 0. In other embodiments, n is 1.

  In some embodiments, p is 0. In other embodiments, p is 1.

In some embodiments, R ^AD is a hydrogen atom. In other embodiments, R ^AD is a (C ₁ -C ₆ ) alkyl group. In some embodiments, R ^AD is a methyl group. For complete clarity, R ^AD may be independently selected from a hydrogen atom and a (C ₁ -C ₆ ) alkyl group, for example, — (CR ^AD R ^AD ) — may be —CH ₂ or -CHCH ₃ - would be.

In some embodiments, the AE is
It is. In other embodiments, the AE is
It is.

R ⁷² is ₁ independently selected from a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, a — (C ₁ -C ₄ ) haloalkyl group, —NO ₂ , F, Br, and Cl in each case. Represents a substituent of ~ 4. For complete clarity, in some embodiments, in each case, R ⁷² can be a hydrogen atom. In other embodiments, R ⁷² can represent four different substituents. In other embodiments, R ⁷² can represent one methyl group and three hydrogen atoms.

In some embodiments, AF is —C (═CH ₂ ) AG. In other embodiments, AF is —C _a H _b F _c , where a is 1-15, b is 0-30, C is 1-31, and b and c are The sum is 2a + 1. In certain embodiments, AF is —C _a F _{2a + 1} or —CH ₂ CF ₃ . In some embodiments, AF is — (R ^d ), wherein — (R ^d ) is an optionally substituted (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group. It is. In other embodiments, AF _{is ^{-C A H B (R d)}} D. When AF is -C _A H _B (R ^d ) _D , R ^d may be optionally substituted with hydrogen or one or more substituents selected from R ⁶¹ and R ⁷¹ ( C ₃ -C ₁₂₎ may be an alicyclic hydrocarbon group. However, at least one example of R ^d must be an optionally substituted (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group. In some embodiments, AF is
It is. In other embodiments, AF is
It is. In some embodiments, AF is — (R ^d ), and — (R ^d ) is optionally substituted with one or more substituents selected from R ⁶¹ and R ⁷¹ . It is an adamantyl group. In other embodiments, AF is — (CH ₂ ) R ^d , wherein R ^d is optionally substituted with one or more substituents selected from R ⁶¹ and R ⁷¹ . It is an adamantyl group.

In some embodiments, AF ^a is —C (═CH ₂ ) AG. In some embodiments, AF ^a is —C (AG) (Q) CH ₂ Q. In some embodiments, AF ^a is —C _a H _b F _c , where a is 1-15, b is 0-30, c is 1-31, b and c Is 2a + 1. In certain embodiments, AF ^a is —C _a F _{2a + 1} or —CH ₂ CF ₃ . In some embodiments, AF ^a is — (R ^da ), wherein — (R ^da ) is optionally substituted (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon. It is a group. In other embodiments, AF ^a is —C _A H _B (R ^da ) _D. When AF ^a is —C _A H _B (R ^da ) _D , R ^da is optionally substituted with a hydrogen atom or one or more substituents selected from R ⁶¹ and R ⁷¹ It can be a (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group. However, at least one example of R ^da must be an optionally substituted (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group. In some embodiments, AF ^a is
It is. In other embodiments, AF ^a is
It is. In some embodiments, AF ^a is — (R ^da ), and — (R ^da ) is optionally substituted with one or more substituents selected from R ⁶¹ and R ^71. An adamantyl group that may be present. In other embodiments, AF ^a is — (CH ₂ ) R ^da , wherein R ^da is optionally substituted with one or more substituents selected from R ^61a and R ^71. An adamantyl group that may be present.

  In some embodiments, A is selected from 1, 2, 3 and 4. In some embodiments, B is selected from an integer between 0 and 1-9. In some embodiments, D is selected from 1, 2, and 3. In some embodiments, the sum of B and D is 2A + 1.

In some embodiments, AG is a hydrogen atom. In other embodiments, AG is F. In other embodiments, AG is CH ₃ . In other embodiments, AG is CF ₃ .

In some embodiments, R ⁶¹ is H, —OH, —CF ₃ , — (C ₁ -C ₄ ) alkyl, —OCH ₃ , —C (═O) OR ^AD , —OC (═O). R ^AD , —C (═O) R ^AD , cyano group, —NO ₂ , F, Cl, Br, —CH ₂ Br, —CH═CH ₂ , —OCH ₂ CH ₂ Br, —OC═OCH═CH ₂ , And —OC═OCCH ₃ ═CH ₂ .

In some embodiments, R 61 ^a is H, —OH, —CF ₃ , — (C ₁ -C ₄ ) alkyl, —OCH ₃ , —C (═O) OR ^AD , —OC (═O). ^{R AD, -C (= O)} R AD, a cyano _{group, -NO 2, F, Cl,} Br, -CH 2 Br, CH = CH 2, -OCH 2 CH 2 Br, -Q, -CH 2 -Q _{, -O-Q, -OCH 2 CH} 2 -Q, -OCH 2 CH 2 O-Q, -CH (Q) CH 2 -Q, -OC = OCH = CH 2, -OC = OCCH 3 = CH 2, -OC = OCHQCH ₂ Q, is selected from -OC = OCCH ₃ QCH ₂ Q.

In some embodiments, R ⁷¹ is H, —CF ₃ , —OH, —OCH ₃ , —C═O (oxo), — (C ₁ -C ₄ ) alkyl, —NO ₂ , F, Br. , Cl, _-C i _{H j (halogen) k,} and _-C s _{H t} represents 1 to 4 substituents independently selected from _(halogen) u -E, wherein, i is 1-2 And j is 0-3, k is 1-5, and the sum of j and k is 2i + 1; and s is 1-2, t is 0-2, u Is 1 to 4, and the sum of t and u is 2s. For complete clarity, in some embodiments, R ⁷¹ can represent 4 hydrogen atoms, while in other embodiments, R ⁷¹ is 1 —CF ₃ , One —CH ₃ and two hydrogen atoms can be represented. In some embodiments, R ⁷¹ can represent —CHF-E. In some embodiments, R ⁷¹ can represent —CF ³ .

In some embodiments, AF is — (R ^d ) or —C _A H _B (R ^d ) _D , or AF ^a is — (R ^da ) or —C _A H _B (R ^da ) _D. ^Where- (R ^d ) or-(R ^da ) is an optionally substituted (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group. In other embodiments, — (R ^d ) or — (R ^da ) is H, —OH, — (C ₁ -C ₄ ) alkyl, —OCH ₃ , —C (═O) O (R ^AD ). , -OC (= O) R ^AD , oxo, -C (= O) R ^AD and 1 or 2 moieties selected from a cyano group. In some embodiments, — (R ^d ) or — (R ^da ) is H, —OH, —CH ₃ , —OCH ₃ , —C (═O) O (CH ₃ ), —OC (═O ) _(CH 3), oxo, substituted by -C (= O) 1 or 2 moieties selected from CH ₃ and a cyano group. In some embodiments, — (R ^d ) or — (R ^da ) is H, —OH, — (C ₁ -C ₄ ) alkyl, —OCH ₃ , —C (═O) O (R ^AD ), —OC (═O) R ^AD , oxo, —C (═O) R ^AD and an adamantyl group substituted with one or two moieties selected from a cyano group. In some embodiments, — (R ^d ) or — (R ^da ) is H, —OH, —CH ₃ , —OCH ₃ , —C (═O) O (CH ₃ ), —OC (═O ) (CH ₃ ), oxo, —C (═O) CH ₃ and an adamantyl group substituted with one or two moieties selected from a cyano group.

In some embodiments, AF is
It is. In some embodiments, AF ^a is
It is.

  In some embodiments, Q is a polymer or oligomer. Several suitable polymers and oligomers and means for attaching residues to those polymers described herein are illustrated in US patent application Ser. No. 12 / 708,958, the relevant portions of which are incorporated herein by reference. Incorporated into.

In some embodiments, G ² is a hydrogen atom, M is an oxygen atom, and AC is —C (═O) NH—. In some embodiments, G ² is a hydrogen atom, M is an oxygen atom, AC is —C (═O) NH—, and AD is a direct bond, — (CR ^AD R ^AD ) ₂ O (C═O) —, — (CH ₂ ) ₂ O—, and
Selected from.

In some embodiments, G ² is a hydrogen atom, M is an oxygen atom, and AC is —C (═O) NH—, and AF or AF ^a is a) —C (═CH ₂ ) AG, b) a phenyl group substituted with R ⁶¹ or R ^61a , c) R ^d or R ^da , and d) — (CH ₂ ) R ^d or — (CH ₂ ) R ^da In these embodiments, R ^d or R ^da is optionally H, —OH, — (C ₁ -C ₄ ) alkyl, —OCH ₃ , —C (═O) O (R ^AD ), —OC. (═O) R ^AD , oxo, —C (═O) R ^AD and an adamantyl group that may be substituted with one or two moieties selected from a cyano group. In some embodiments, G ² is a hydrogen atom, M is an oxygen atom, AC is —C (═O) NH—, and AD is a direct bond, — (CR ^AD R R _{^{AD) 2 O (C = O}} ) -, - (CH 2) 2 O-, and
And AF or AF ^a is a) —C (═CH ₂ ) AG, b) a phenyl group substituted with R ⁶¹ or R ^61a , c) R ^d or R ^da , and d) — (CH ₂ ) selected from R ^d or — (CH ₂ ) R ^da In these embodiments, R ^d or R ^da is H, —OH, — (C ₁ -C ₄ ) alkyl, —OCH ₃ , —C (═O) O (R ^AD ), —OC (═O ) R ^AD , oxo, —C (═O) R ^AD , and an adamantyl group that may be optionally substituted with one or two moieties selected from a cyano group.

In some embodiments, G ² is a hydrogen atom; M is an oxygen atom; AC is —C (═O) O—; AD is a direct bond; and AF or AF ^a is selected from R ^d , R ^da , — (CH ₂ ) R ^d , and — (CH ₂ ) R ^da . In these embodiments, R ^d or R ^da is H, —OH, — (C ₁ -C ₄ ) alkyl, —OCH ₃ , —C (═O) O (R ^AD ), —OC (═O ) R ^AD , oxo, —C (═O) R ^AD and an adamantyl group optionally substituted with one or two moieties selected from a cyano group.

In some embodiments, G ² is a hydrogen atom; M is an oxygen atom; AC is —CH ₂ O—; AD is a direct bond, and —C (═O) —. And AF or AF ^a is —C (═CH ₂ ) AG.

In some embodiments, AC is —C (═O) NR ^AC ; and AD is a direct bond, — (CR ^AD R ^AD ) _m O (C═O) —, — (CH ₂ ) ₂ O—. , And -AE (O) _n (C = O) _p- . In some embodiments, AC is C (═O) NR ^AC ; and AD is a direct bond, — (CR ^AD R ^AD ) ₂ O (C═O) —, —C (═O) —, — _{(CH 2)} 2 O-, and
Selected from.

In some embodiments, the present invention relates to a compound selected from the table below.

  As used herein, an alkyl group is intended to include linear, branched or cyclic saturated hydrocarbon structures and combinations thereof. A combination would be, for example, cyclopropylmethyl. Cycloalkyl groups are part of alkyl groups and include cyclic hydrocarbon groups of 3 to 8 carbon atoms. Examples of the cycloalkyl group include a c-propyl group, a c-butyl group, a c-pentyl group, and a norbornyl group.

A silaalkane (or silaalkyl) group means an alkyl residue in which one or more carbon atoms have been replaced by silicon atoms. Examples include trimethylsilylmethyl [(CH ₃ ) ₃ SiCH ₂ —] and trimethylsilane [(CH ₃ ) ₃ Si—] groups.

A hydrocarbon group is a substituent containing a hydrogen atom and a carbon atom as the only elemental component, and therefore, for example, an alkyl group, a cycloalkyl group, a polycycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like It includes _C 1 _{-C 20} hydrocarbon group comprising a combination of. Examples include benzyl, phenyl, ethyl, phenethyl, cyclohexylmethyl, adamantyl, and naphthylethyl groups. For complete clarity, the (C ₁ -C ₈ ) hydrocarbon group has 1, 2, 3, 4, 5, 6, 7 or 8 carbons and the appropriate number of hydrogen atoms to satisfy the valence. The part to include. The term “carbocycle” is intended to include a ring system consisting entirely of carbon atoms but in any oxidation state. _Thus, (C 3 _{-C 12)} carbocycle cyclopropane, benzene, adamantyl, and refers to the system, such as _cyclohexene; (C 8 _{-C 12)} carbon polycyclic (carbopolycycle) norbornane, decalin, indane and naphthalene Such a system is meant.

  Alkoxy or alkoxyl means a group of 1 to 8 carbon atoms in a straight chain, branched chain, cyclic structure and combinations thereof bonded to the parent structure through an oxygen atom. Examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, cyclopropyloxy group, cyclohexyloxy group and the like. A lower alkoxy group means a group containing 1 to 4 carbon atoms.

  An oxaalkyl group means an alkyl residue in which one or more carbon atoms (and hydrogen atoms bonded to them) are replaced by oxygen atoms. Examples include methoxy group, methoxypropoxy group, 3,6,9-trioxadecyl group and the like. The term oxaalkyl has the meaning as it is understood in the art [see Naming and Indexing of Chemical Substrates for Chemical Abstracts, published by the American Chemical Society, ¶ 197, limited to None], that is, a compound in which an oxygen atom is bonded to an adjacent atom via a single bond (forms an ether bond); a double-bonded oxygen atom, as found in a carbonyl group, does not. Similarly, a thiaalkyl group and an azaalkyl group mean an alkyl residue in which one or more carbon atoms are replaced by a sulfur atom or a nitrogen atom, respectively. Examples include an ethylaminoethyl group and a methylthiopropyl group.

  Acyl group means a linear, branched, cyclic structure, saturated, unsaturated, aromatic and combinations thereof of 1 to 8 carbon atoms bonded to the parent structure via a carbonyl function. To do. An acyl group also refers to a formyl group having only hydrogen atoms bonded to the parent structure through a carbonyl function. One or more carbon atoms of the acyl residue can be replaced with a nitrogen atom, oxygen atom or sulfur atom so long as the point of attachment to the parent structure remains in the carbonyl group. Examples include acetyl group, benzoyl group, propionyl group, isobutyryl group, t-butoxycarbonyl group, benzyloxycarbonyl group and the like. A lower acyl group means a group containing 1 to 4 carbon atoms.

  Aliphatic refers to an unsaturated hydrocarbon substituent. Aliphatic substituents can be cyclic (such as cyclopentane or adamantyl) or acyclic, and can be saturated or unsaturated bonds (eg, they are linear or branched alkanes, alkenes, or alkynes). Can be included.

  The aryl group and heteroaryl group are selected from a 5- or 6-membered aromatic or heteroaromatic group containing 0 to 3 heteroatoms selected from O, N, or S; O, N, or S A bicyclic 9 or 10-membered aromatic or heteroaromatic group containing 0 to 3 heteroatoms; or a tricyclic 13 containing 0 to 3 heteroatoms selected from O, N or S Alternatively, it means a 14-membered aromatic ring system group or a heteroaromatic ring system group. Examples of aromatic 6-14 membered carbocyclic rings include, for example, benzene, naphthalene, indane, tetralin, and fluorene. Examples of 5-10 membered aromatic heterocyclic rings include, for example: Mention may be made of imidazole, pyridine, indole, thiophene, benzopyranone, thiazole, furan, benzimidazole, quinoline, isoquinoline, quinoxaline, pyrimidine, pyrazine, tetrazole and pyrazole.

  An arylalkyl group means a substituent in which an aryl residue is bonded to the parent structure through an alkyl group. Examples are benzyl, phenethyl and the like. A heteroarylalkyl group refers to a substituent in which a heteroaryl residue is attached to the parent structure through an alkyl group. Examples include a pyridinylmethyl group, a pyrimidinylethyl group, and the like.

  A heterocyclic group means a cycloalkyl or aryl residue in which 1 to 3 carbon atoms are replaced by a heteroatom selected from the group consisting of N, O and S. Nitrogen and sulfur heteroatoms can optionally be oxidized, and nitrogen heteroatoms can optionally be quaternized. Examples of heterocyclic groups within the scope of the present invention include pyrrolidine, pyrazole, pyrrole, indole, quinoline, isoquinoline, tetrahydroisoquinoline, benzofuran, benzodioxan, benzodioxole (generally methylene if present as a substituent) (Referred to as dioxyphenyl), tetrazole, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furan, oxazole, oxazoline, isoxazole, dioxane, tetrahydrofuran and the like. Note that heteroaryl is part of a heterocycle where the heterocycle is aromatic. Examples of heterocyclyl residues further include piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxo-pyrrolidinyl, 2-oxoazepinyl, azepinyl, 4-piperidinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazinyl, Oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, benzimidazolyl, thiadiazolyl, benzopyranyl, benzothiazolyl, tetrahydrofuryl, tetrahydropyranyl, thienyl, benzothienyl, thiamorpholinyl, thiamorpholinyl sulfoxide, thiamorpholinyl sulfoxide Mention may be made of folinyl sulfone, oxadiazolyl, triazolyl and tetrahydroquinolinyl. An oxygen heterocycle group is a heterocycle containing at least one oxygen atom in the ring; it can contain additional oxygen atoms as well as other heteroatoms. A sulfur heterocycle group is a heterocycle containing at least one sulfur atom in the ring; it can contain additional sulfur atoms as well as other heteroatoms. An oxygen heteroaryl group is part of an oxygen heterocyclic group; examples include furan and oxazole. Sulfur heteroaryl groups are part of sulfur heterocyclic groups; examples include thiophene and thiazine. A nitrogen heterocycle group is a heterocycle containing at least one nitrogen atom in the ring; it can contain additional nitrogen atoms as well as other heteroatoms. Examples include piperidine, piperazine, morpholine, pyrrolidine and thiomorpholine. Nitrogen heteroaryl groups are part of nitrogen heterocyclic groups; examples include pyridine, pyrrole and thiazole.

  As used herein, the term “optionally substituted” can be used interchangeably with “unsubstituted or substituted”. “Substituted” means substitution by one or more particular groups of hydrogen atoms of a particular group. For example, in the substituted alkyl group, aryl group, cycloalkyl group, heterocyclyl group and the like, one or more H atoms of each residue are halogen atoms, haloalkyl groups, alkyl groups, acyl groups, alkoxyalkyl groups, Hydroxy lower alkyl group, carbonyl group, phenyl group, heteroaryl group, benzenesulfonyl group, hydroxy group, lower alkoxy group, haloalkoxy group, oxaalkyl group, carboxy group, alkoxycarbonyl [—C (═O) O-alkyl] Group, cyano group, acetoxy group, nitro group, mercapto group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, aryl group, benzyl group, oxaalkyl group, and alkyl group, aryl group substituted with benzyloxy group, A cycloalkyl group or heterocyclyl Means a ru group. “Oxo groups” are also included in the substituents shown in “optionally substituted”; however, since the oxo group is a divalent group, it may not be suitable as a substituent (for example, Those skilled in the art will understand that (in the phenyl group). In one embodiment, one, two or three hydrogen atoms are replaced with a specific group. In the case of alkyl groups, cycloalkyl groups and aryl groups, 4 or more hydrogen atoms can be replaced by fluorine atoms; in fact, all available hydrogen atoms can be replaced by fluorine atoms.

  The term “halogen atom” means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Where two numbers are used for the term “integer between”, it includes the two specified and any integer in between. For example, the term “integer between 1 and 4” indicates that any integer selected from 1, 2, 3, or 4 is included.

  Some of the compounds described herein contain one or more asymmetric centers and can therefore be defined as (R)-or (S)-from the standpoint of absolute stereochemistry. Enantiomeric, diastereomeric, and other stereoisomeric forms can occur. Unless defined otherwise, the invention includes all such possible isomers, as well as their racemic and optically pure forms. Optically active (R)-and (S) -isomers, or (D)-and (L) -isomers, can be prepared using chiral synthons or chiral reagents, or using conventional techniques. Can be split using. Where a compound described herein contains an olefinic double bond or other geometric asymmetric center, the compound shall include both the E and Z geometric isomers, unless otherwise specified. Similarly, all tautomeric forms are also intended to be included.

  The forms of carbon-carbon double bonds other than the endocyclic double bond appearing herein are selected for convenience only and are not intended to indicate a particular form; The carbon-carbon double bond, optionally expressed as trans, can be cis, trans, or a mixture of these two in any proportion.

  Terms relating to “protected”, “deprotected” and “protected” functionalities appear in several places throughout the specification. Such terms are well understood by those skilled in the art and are used in the context of processes involving sequential processing with a series of reagents. In that context, a protecting group refers to a group that is used to mask a functional group during a process step that would otherwise cause a reaction, but where the reaction is undesirable. The protecting group interferes with the reaction in the process but can subsequently be removed to expose the original functional group. Removal or “deprotection” occurs after completion of the reaction (s) that the functional group will interfere with. Thus, when a series of reagents are identified, such as in the process of the present invention, one skilled in the art can readily envision groups that are suitable as “protecting groups”.

The following abbreviations and terms have the indicated meaning throughout this specification:
Ac = acetyl BNB = 4-bromomethyl-3-nitrobenzoic acid Boc = t-butyloxycarbonyl Bu = butyl c- = cycloDBU = diazabicyclo [5.4.0] undes-7-ene DCM = dichloromethane = methylene chloride = CH ₂ Cl ₂
DEAD = diethylazodicarboxylate DIC = diisopropylcarbodiimide DIEA = N, N-diisopropylethylamine DMAP = 4-N, N-dimethylaminopyridine DMF = N, N-dimethylformamide DMSO = dimethyl sulfoxide DVB = 1,4-divinylbenzene EEDQ = 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline ESCAP = environmentally stable chemically amplified photoresist Et = ethyl Fmoc = 9-fluorenylmethoxycarbonyl GC = gas chromatography HATU = O- ( 7-azabenzotriazol-1-yl) -1,1,3,3-
Tetramethyluronium hexafluorophosphate HOAc = acetic acid HOBt = hydroxybenzotriazole Me = methylmesyl = methanesulfonyl Ms = mesyl MTBE = methyl t-butyl ether NMO = N-methylmorpholine oxide-OTf = triflate = trifluoromethanesulfonate = —OSO ₂ CF ₃
PEB = post-exposure bake PEG = polyethylene glycol Ph or κ = phenyl PhOH = phenol PfP = pentafluorophenol PPTS = pyridinium p-toluenesulfonate PyBroP = bromo-tris-pyrrolidino-phosphonium hexafluorophosphate
Rt = room temperature sat'd = saturated s- = second t- = third TBDMS = t-butyldimethylsilyl-Tf = trifil = trifluoromethylsulfonyl = -SO ₂ CF ₃
Triflate = -OTf = -OSO ₂ CF ₃
TFA = trifluoroacetic acid Tg = glass transition temperature THF = tetrahydrofuran TMOF = trimethyl orthoformate TMS = trimethylsilyl tosyl = Ts = p-toluenesulfonyl = -SO ₂ - para _{- (C 6} H 4) -C
H ₃
Tosylate = -OTs = -OSO ₂ - p _{- (C 6 H 4) -CH} 3
Trt = triphenylmethyl

  A comprehensive list of abbreviations used by organic chemists (ie, those skilled in the art) can be found in the first issue of each volume of the Journal of Organic Chemistry. The list typically presented in the table entitled “Standard List of Abbreviations” is incorporated herein by reference.

When referring to acid strength, or equivalently, pK _a value herein, the value determined by Taft parameter analysis, especially when referring to sulfonic acid and / or acid generated by photolysis, This analysis itself is known in the art and is described, for example, in: Cameron et al., “Structural Effects of Photoacid Generators on Deep UV Resistance”, Society of Plastic Engineers, Inc. Proceedings. "Photopolymers, Principles, Processes and Materials", 11th International Conference, pp. 120-139 (1997) and J.A. P. Guthrie, Can. J. et al. Chem. 56: 2342-354 (1978). As reported in U.S. Pat. No. 6,803,169, Hots (paratoluenesulfonic acid) have a pK _a of -2.66 as determined by Taft parameter analysis. Thus, acids that are at least as strong as HOTs have _a pKa of -2.66 or less as determined by Taft parameter analysis.

The term “sulfonic acid precursor” as used herein means a molecule that can decompose under acidic conditions to generate HOSO ₂ R ³ .

  The term “photoresist polymer” as used herein means a polymer that can act as a major component in a photoresist.

  The term “photoresist substrate”, as used herein, is suitable for use as a substrate in photolithography or other similar processes, and thus photo applied to the substrate as part of a photolithography process. It refers to an article that can have a resist, for example, a silicon wafer.

  The term “photoresist composition” as used herein means a composition that can be used in connection with photolithography.

  As is known in the art, ESCAP (Environmentally Stable Chemically Amplified Photoresist) polymers undergo well known acid catalyzed reactions. A central feature of these chemical systems is that the acidolysis reaction occurs only in the presence of an acid, i.e., catalytically, at a temperature above the normal post-exposure bake temperature used in integrated circuit manufacturing, i. Except when the temperature is 65-140 ° C., it does not occur thermally without acid. Other types of chemically amplified resists (often referred to as low activation energy resists) can use low post-exposure temperatures of about 20-120 ° C.

The sulfonic acid precursor provided or used in accordance with embodiments of the present invention can be viewed as an acid amplifying agent having two parts, a “trigger” and a sulfonate group. A “trigger” is a leaving group attached to the remainder of the molecule that is pyrolytically stable at the temperature at which the substrate is processed, but is protonated in the presence of an acid. And leaving groups that are sufficiently unstable to allow removal of protons to form carbon-carbon double bonds. One general but non-limiting illustration is provided in Reaction Scheme 1. As shown in Reaction Scheme 1, in some embodiments of the invention, the leaving group is at the carbon labeled γ position and the sulfonate is at the carbon labeled α position, ie, There is a hydrogen-carrying carbon atom between the carbon atom to which the leaving group and the sulfonate group are bonded.

As illustrated schematically in Reaction Scheme 1, as a result of removal of the leaving group, the sulfonate becomes an allyl sulfonate activated for dissociation with respect to the alkyl sulfonate that was present prior to removal of the leaving group. . Dissociation of the sulfonate moiety and disappearance of the proton results in a conjugated π system. This is shown in a non-limiting manner in Reaction Scheme 2, where R ^{1 *} , R ^{2 *} and R ^{5 *} represent R ¹ , R ² and R ⁵ , respectively, which have lost a proton.

  Photoresist polymers, ie, polymers suitable for use with photoacid generators and / or acid amplifiers in the manufacture of photoresists are well known in the art. For example, U.S. Patent No. 6,617,086, U.S. Patent No. 6,803,169, U.S. Patent Application Publication No. 2003/0134227, U.S. Patent Application, the entire contents of which are incorporated herein by reference. See publication 2005/0147916. For example, by way of illustration, US Pat. No. 6,803,169 describes a variety of “deblocking resins” in that specification that are suitable for forming photoresists, particularly positive photoresists. The polymers of are described. In that specification, such polymers can be “acid-labile groups”, ie moieties that can be easily removed by acid, “suitably pendant groups from the polymer backbone, For example, acid sensitive esters, carbonates, acetals, ketals, etc. Acid labile groups essential to the polymer backbone can also be used. The portion of the polymer from which acid labile groups have been removed by contact with the acid generated by photolysis is susceptible to dissolution by the base during development of the photoresist. As described therein, deblocking resins are disclosed in European Patent Application Publication No. EP0813113A1 (corresponding to US Pat. No. 5,861,231), European Patent Application No. 97115532 (US Pat. No. 5,861,231). US Pat. No. 5,258,257, US Pat. No. 4,968,581, US Pat. No. 4,883,740, US Pat. No. 4,810,613, US Pat. No. 4,491, It can be a deblocking resin described in 628 and 5,492,793. According to further description in US Pat. No. 6,803,169:

“Examples of preferred deblocking resins for use in the resists of the present invention include polymers containing both phenolic and non-phenolic units. For example, one preferred group of such polymers has acid labile groups substantially, essentially or completely only in the non-phenolic units of the polymer. One preferred polymer binder has the formula:
[Wherein the hydroxyl group is present in the ortho, meta or para position throughout the polymer and R ′ is from 1 to about 18 carbon atoms, more typically from 1 to about 6 to 8 carbon atoms. Is a substituted or unsubstituted alkyl group having a repeating unit of x and y. A tert-butyl group is a commonly used R ′ group. The R ′ group is optionally substituted, for example, with one or more halogen atoms (especially F, Cl or Br atoms), C _1-8 alkoxy groups, C _2-8 alkenyl groups, etc. be able to. The indicated phenolic units of the polymer can optionally be substituted with such groups. The units x and y can be regularly alternated in the polymer or can be randomly scattered in the polymer. Such copolymers can be easily formed. For example, for a resin of the above formula, vinyl phenol and a substituted or unsubstituted alkyl acrylate, such as t-butyl acrylate, can be condensed under free radical conditions known in the art. The substituted ester moiety in the acrylate unit, i.e. R'-O-C (= O)-, serves as an acid labile group of the resin and when the photoresist coating layer containing the resin is exposed. Undergoes photoacid-induced cleavage. Copolymer, from about 3,000 to about 50,000, for example, have about 10,000 to about 30,000 _{M w,} can the molecular weight distribution of about 3 or less; in some embodiments, the molecular weight The distribution can be 2 or less. Such copolymers can be made by such free radical polymerization or other known methods, suitably having a _{Mw of} about 3,000 to about 50,000 and a molecular weight distribution of about 3 or less, some embodiments Having a molecular weight distribution of about 2 or less.

Further preferred deblocking resins have acid labile groups on both the phenolic and non-phenolic units of the polymer. One typical polymer binder has the formula:
[Wherein the R ′ group is a photoacid labile group as defined above for other typical polymers; X may or may not contain a photoacid labile group. Each of Y is independently a hydrogen atom or a C _1-6 alkyl group, preferably a hydrogen atom or a methyl group], and has repeating units a, b and c. . The values a, b and c indicate the molar amount of polymer units. These polymer units can be regularly alternated in the polymer or can be randomly scattered in the polymer. Suitable X groups can be aliphatic or aromatic groups such as phenyl, cyclohexyl, adamantyl, isobornyl acrylate, methacrylate, isobornyl methacrylate, and the like. Such polymers can be formed in the same manner as described above for the polymer, and the formed copolymer provides phenolic acid labile groups upon reaction.

Further deblocking resins contribute to the aqueous developability of photoresists comprising 1) units containing acid labile groups; 2) units containing no reactive groups and hydroxy groups; and 3) polymers as resin binders. It contains at least three separate repeat units of aromatic units or other units. Corresponding as a specific example of this type of deblocking polymer ''
[Wherein R in unit (1) is preferably a substituted or unsubstituted alkyl group having 1 to about 10 carbon atoms, more typically 1 to about 6 carbon atoms]. . A branched alkyl group, such as a tert-butyl group, is a typical R group. The polymer can also include a mixture of various R groups, for example, by using various acrylate monomers during polymer synthesis.

The R ^b groups in the unit (2) of the above formula are each independently substituted or unsubstituted having, for example, halogen atoms (especially F atoms, Cl atoms and Br atoms), preferably having 1 to about 8 carbon atoms. Alkyl groups, preferably substituted or unsubstituted alkoxy groups having 1 to about 8 carbon atoms, preferably substituted or unsubstituted alkenyl groups having 2 to about 8 carbon atoms, preferably 2 to about 8 carbon atoms. Substituted or unsubstituted alkynyl groups, preferably substituted or unsubstituted alkylthio groups having from 1 to about 8 carbon atoms, cyano groups, nitro groups, etc .; q is 0 (the phenyl ring is completely To an integer of from 5 to, for example, 0, 1 or 2. Also, two R ^b groups on adjacent carbon atoms taken together can be one, two or three having 4 to about 8 ring members per ring (with ring carbon atoms to which they are attached). The above condensed aromatic ring or alicyclic ring can be formed. For example, two R ^b groups can be taken together to form a naphthyl or acenaphthyl ring (with the indicated phenyl group). By using various substituted or unsubstituted vinylphenyl monomers during polymer synthesis as in unit (1), the polymer has different R ^b groups or no R ^b groups (ie, q = 0) may contain mixtures of various units (2).

Each R ^a group of unit (3) of the above formula (A) is independently substituted, for example with halogen (especially F, Cl and Br atoms), preferably having 1 to about 8 carbon atoms. Or an unsubstituted alkyl group, preferably a substituted or unsubstituted alkoxy group having 1 to about 8 carbon atoms, preferably a substituted or unsubstituted alkenyl group having 2 to about 8 carbon atoms, preferably 1 carbon atom substituted or unsubstituted sulfonyl group having from about 8 to, for example, mesyl group _{(CH 3} SO 2 O-), substituted or unsubstituted alkyl ester group, for example, RCOO- (wherein, R is preferably Preferably an alkyl group having 1 to about 10 carbon atoms), preferably a substituted or unsubstituted alkynyl group having 2 to about 8 carbon atoms, preferably 1 to about 8 carbon atoms. The Substituted or unsubstituted alkylthio groups, cyano groups, nitro groups, etc .; p is an integer from 0 (when the phenyl ring has one hydroxy substituent) to 4 such as 0, 1 or 2. Also, two R ^a groups on adjacent carbons can be combined together (with ring carbon atoms to which they are attached) one, two or three having from 4 to about 8 ring members per ring. The above condensed aromatic ring or alicyclic ring can be formed. For example, two R ^a groups can be taken together to form a naphthyl or acenaphthyl ring (with a phenol group shown in Formula (A)). By using various substituted or unsubstituted vinyl phenyl monomers during polymer synthesis, as in unit (A), the polymer has different R ^a groups or no R ^a groups (ie, p = 0) may comprise a mixture of various units (3). As shown in formula (A) above, the hydroxyl group of unit (3) can be in either the ortho, meta or para position throughout the copolymer. Para or meta substitution is generally preferred.

R ^a , R ^b and R ^c substituents are each independently a hydrogen atom, or preferably 1 to about 8 carbon atoms, more typically 1 to about 6 carbon atoms, or more preferably a carbon atom. It can be a substituted or unsubstituted alkyl group having 1 to about 3.

The substituted groups described above (ie, the substituted groups R and R ^{a to} R ^{e of} formula (I) above) are one or more suitable positions at one or more available positions. A group such as a halogen atom (especially an F atom, a Cl atom or a Br atom); a C _1-8 alkyl group; a C _1-8 alkoxy group; a C _2-8 alkenyl group; a C _2-8 alkynyl group; For example, it can be substituted by a phenyl group; an alkanoyl group, for example, a C _1-6 alkanoyl group such as acyl; Typically, the substituted moiety is substituted at one, two or three available positions.

  In the above formula (A), x, y and z are respectively the mole fraction or percentage of the units (3), (2) and (1) in the copolymer. These mole fractions can vary suitably over a fairly wide range of values, for example, x can suitably be about 10 to 90 percent, more preferably about 20 to 90 percent; y Can suitably be about 1-75 percent, more preferably about 2-60 percent; and z can be about 1-75 percent, more preferably about 2-60 percent. it can.

  As a preferred copolymer of the above formula (A), only the polymer unit corresponds to the general structure represented by the units (1), (2) and (3), and the sum of the mole percentages x, y and z is equal to 100 Things can be mentioned. Preferably, however, these units (1), (2) and (3) still constitute the major part of the copolymer, but for example the sum of x, y and z is at least about 50 percent (ie units ( 1), (2) and (3) at least 50 mole percent of the polymer), more preferably, the sum of x, y and z is at least about 70 percent, and even more preferably the sum of x, y and z Is at least about 80 or 90 percent, however, preferred polymers may also contain additional units, where the sum of x, y and z is less than 100. For a detailed disclosure of the free radical synthesis of the copolymer of formula (A) above, reference is made to European Patent Application Publication No. EP0813113A1 (corresponding to US Pat. No. 5,861,231).

  Further resin binders may include those having an acetal ester and / or ketal ester deblocking group. Such resins are available from Shipley and U.S. Pat. Kumar EP0829766A2 (corresponding to US Pat. No. 6,090,526). For example, suitable resins include terpolymers formed from hydroxystyrene, styrene and acid labile components such as 1-propyloxy-1-ethyl methacrylate.

  Further preferred polymers are disclosed in US Pat. No. 6,136,501.

According to US Pat. No. 6,803,169, “the polymers of the present invention can be produced by various methods. While the reaction temperature may vary depending on the reactivity of the particular reagent used and the boiling point of the reaction solvent (if a solvent is used), one suitable method is for example an inert atmosphere (eg Free radical polymerization by reacting selected monomers in the presence of a radical initiator to provide the various units discussed above at high temperatures, eg, above about 70 ° C., under N ₂ or argon). It is. Examples of suitable reaction solvents include tetrahydrofuran, dimethylformamide and the like. Suitable reaction temperatures for any particular system can be readily determined empirically by those skilled in the art based on the present disclosure. Monomers that can be subjected to a reaction to give a polymer of the present invention can be readily identified by those skilled in the art based on the present disclosure. For example, suitable monomers include acrylate (including methacrylate), t-butyl acrylate, acrylonitrile, methacrylonitrile, itaconic anhydride, and the like. Various free radical initiators can be used to produce the copolymers of the present invention. For example, an azo compound such as azo-bis-2,4-dimethylpentanenitrile can be used. Peroxides, peresters, peracids and persulfates can also be used.

Unless otherwise specified, the polymers used as the resin binder component of the resists of the present invention typically have a weight average molecular weight (M _w ) of 1,000 to about 100,000, more preferably about 2,000 to It has about 30,000, still more preferably about 2,000-15,000 or 20,000, and has a molecular weight distribution ( _Mw / _Mn ) of about 3 or less, more preferably a molecular weight distribution of about 2 or less. The molecular weight (M _w or M _n ) of the polymers of the present invention is suitably determined by gel permeation chromatography.

Preferred polymers exhibit a _Tg that is high enough to facilitate the use of the polymer in photoresists. Thus, preferably the polymer has a T _g higher than a typical soft bake (solvent removal) temperature, eg, a T _g higher than about 100 ° C., more preferably a T _g higher than about 110 ° C., even more preferably Having a T _g higher than about 120 ° C.

  For 193 nm imaging applications, preferably, the resist resin binder component is substantially free of any phenyl groups or other aromatic groups. For example, preferred polymers for use in 193 imaging are less than about 1 mole percent aromatic groups, more preferably less than about 0.1, 0.02, 0.04 and 0.08 mole percent aromatic groups. Even more preferably, it contains less than about 0.01 mole percent aromatic groups. Particularly preferred polymers do not contain any aromatic groups. Aromatic groups are strongly undesirable for polymers used in photoresists imaged at 193 nm because they can strongly absorb radiation below 200 nm. ]

  The photoresist can also include other materials. Examples of other optical additives include actinic dyes and contrast dyes, anti-strain agents, plasticizers, and speed enhancers. Such optical additives are generally photoresist compositions, except for fillers and dyes, which can be present in relatively large concentrations, for example, in amounts of 5-30% by weight of the total dry components of the resist. Present in small concentrations. Common additives are basic compounds such as tetrabutylammonium hydroxide (TBAH), tetrabutylammonium lactate, or tetrabutylammonium acetate, which can increase the resolution of the developed image. For resists imaged at 193 nm, typical bases are hindered amines such as diazabicycloundecene, diazabicyclononene, or diterbutylethanolamine. Such amines may suitably be present in an amount of about 0.03 to 5 to 10% by weight, based on the total solids of the resist composition (all components except the solvent).

  It is preferred that the PAG blend component be present in the photoresist formulation in an amount sufficient to produce a latent image in the resist coating layer. More particularly, the PAG blend is suitably from about 0.5 to 40% by weight of the total solids of the resist composition, more generally from about 0.5 to 10% by weight of the total solids of the resist composition. Present in the amount of. The individual PAGs of the blend can suitably be present in approximately equimolar amounts in the resist composition, or each PAG can be present in different molar amounts. However, it is generally preferred that each type or type of PAG is present in an amount of at least about 20-25 mole percent of the total PAG present in the resist formulation.

  The resin binder component of the resist is generally used in an amount sufficient to make the exposed coating layer of the resist developable, for example with an aqueous alkaline solution. More particularly, the resin binder suitably comprises 50 to about 90 weight percent of the total solids of the resist.

  Photoresists are generally manufactured according to known methods. For example, the resist may be a suitable solvent, such as a glycol ether such as 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; lactate such as ethyl lactate or methyl lactate. (Preferably ethyl lactate); propionate, especially methyl propionate, ethyl propionate and ethyl ethoxypropionate; cellosolve ester, eg methyl cellosolve acetate; aromatic hydrocarbon, eg toluene or xylene; ketone Manufactured as a coating composition by dissolving the components of the photoresist in, for example, methyl ethyl ketone or cyclohexanone; It is it is possible. In general, the solids content of the photoresist varies from 5 to 35% by weight of the total weight of the photoresist composition.

  The photoresist can be used according to known methods. The photoresist can be applied as a dry film, but preferably the photoresist is applied to the substrate as a liquid coating composition, preferably heated to remove the solvent until the coating layer is tack free. And exposed to activating radiation through a photomask, and optionally post-baked to provide or enhance the solubility difference between exposed and unexposed areas of the resist coating layer, and Preferably, the image is developed using an aqueous alkaline developer to form a relief image.

  The substrate may suitably be any substrate used in processes involving photoresist, such as a microelectronic wafer. For example, the substrate can be a silicon, silicon dioxide, or aluminum-aluminum oxide microelectronic wafer. Gallium arsenide, ceramic, quartz and copper substrates can also be used. Substrates used for liquid crystal displays and other flat panel display applications such as glass substrates, indium tin oxide coated substrates and the like are also used. As discussed above, highly resolved relief images can be formed on substrates that may be difficult to pattern fine images, such as boron phosphosilicate glass. Was found. The liquid coating resist composition can be applied by any standard means, such as spinning, dipping or roller coating.

  Rather than applying the resist composition directly on the substrate surface, a coating layer of the antireflective coating composition is first applied on the substrate surface, and a photoresist coating layer is applied on the antireflective underlayer coating. it can. A number of anti-reflective coating compositions can be used, examples of which include those disclosed in European Patent Application Publication Nos. 0542008A1 and 0813114A2 (both are Shipley). For resists imaged at 248 nm, preferably an antireflective composition comprising a resin binder having anthracene units can be used.

The exposure energy must be sufficient to effectively activate the photoactive component of the radiation sensitive system and produce a patterned image on the resist coating layer. Suitable exposure energy is generally in the range of about 10 to 300 mJ / cm ² . Exposure wavelengths in the deep ultraviolet range, especially 250 nm or less or 200 nm or less, for example, about 248 nm or 193 nm, are often used for the photoresists described herein. The exposed resist coating layer can be thermally processed at a suitable post-exposure bake temperature that is, for example, about 50 ° C. or more, more specifically about 50-160 ° C. after exposure and before development. After development, the substrate surface exposed by development can then be selectively processed, for example, the exposed substrate region of the photoresist is chemically etched or plated according to procedures known in the art. be able to. Suitable etchants may include hydrofluoric acid etching solution and plasma gas etch, such as oxygen plasma etch.

  Thus, in embodiments of the present invention, photoresist polymers known in the art such as those described in US Pat. No. 6,803,169 or references cited therein and above Those listed in the quoted text can be used. The resists themselves according to embodiments of the present invention are similarly prepared according to methods known in the art, such as those described in US Pat. No. 6,803,169, for example, suitable solvents such as glycol ethers. For example, 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; lactate such as ethyl lactate or methyl lactate; propionate, especially methyl propionate, ethyl propio And ethyl ethoxypropionates; cellosolve esters such as methyl cellosolve acetate; aromatic hydrocarbons such as toluene or xylene; ketones such as methyl ethyl ketone or cyclohexane Non; dissolving the components of the photoresist in such; by baking to impart the solution to the substrate, can be prepared. In general, the solids content of the photoresist varies from 5 to 35% by weight of the total weight of the photoresist composition.

In some embodiments, the sulfonic acid precursor can be included in the photoresist composition as a molecule separate from the polymer. In other embodiments, the sulfonic acid precursor can be incorporated into the polymer chain. For example, a photoresist polymer as defined in US Pat. No. 6,803,169 has the following structure:
R ′ can be a sulfonic acid precursor. This is, for example, the following formula in a mixture of monomers used to produce the polymer:
[In the above formula, AA, G ¹ , G ² , and AB are defined in this specification], and the compound is thus incorporated into the polymer main chain. Can be achieved. If another acrylic acid-derived monomer containing a different group R ′, for example a tert-butyl group, is also used in the polymer synthesis, a quadpolymer is provided rather than the indicated terpolymer. Alternatively, a small amount of cadpolymer (or terpolymer) incorporating a sulfonic acid generating compound (only) can be synthesized, and this cadpolymer or terpolymer in the manufacture of a photoresist, where R ′ is a sulfonic acid It can be blended with large amounts of terpolymers that are not generating groups.

  The amount of sulfonic acid precursor used should be up to 40 mol% of the solids content of the photoresist composition, for example 1-30 mol%, e.g. 2-20 mol% of the solids content of the photoresist composition. Can do. If the sulfonic acid precursor is incorporated into the polymer, the monomer can constitute up to 40 mol% of the polymer, for example 1-30% mol% or 2-20% mol%.

  In some embodiments of the present invention, the photoresist composition comprises a photoacid generator (PAG). PAGs are well known in the art, for example, EP0164248, EP0232972, EP717319A1, US Pat. No. 4,442,197, US Pat. No. 4,603,101, US Pat. No. 4,624,912, US Pat. No. 5,558,976, US Pat. No. 5,879,856, US Pat. No. 6,300,035, US Pat. No. 6,803,169 and US Patent Application Publication No. 2003/0134227 See, for example, the following: di- (t-butylphenyl) iodonium triflate, di- (t-butyl), the entire contents of which are incorporated herein by reference. Phenyl) iodonium perfluorobutanesulfonate, di- (4-tert-butylphenyl) iodonium per Luooctane sulfonate, di- (4-t-butylphenyl) iodonium o-trifluoromethylbenzene sulfonate, di- (4-t-butylphenyl) iodonium camphorsulfonate, di- (t-butylphenyl) iodonium perfluorobenzene Sulfonate, di- (t-butylphenyl) iodonium p-toluenesulfonate, triphenylsulfonium triflate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium o-trifluoromethylbenzenesulfonate, triphenylsulfonium perfluorobutanesulfonate Phenylsulfonium camphorsulfonate, triphenylsulfonium perfluorobenzenesulfonate, triphenylsulfonium -Toluenesulfonate, N-[(trifluoromethanesulfonyl) oxy] -5-norbornene-2,3-dicarboximide, N-[(perfluorobutanesulfonyl) oxy] -5-norbornene-2,3-dicarboximide N-[(perfluorooctanesulfonyl) oxy] -5-norbornene-2,3-dicarboximide, N-[(o-trifluoromethylbenzenesulfonyl) oxy] -5-norbornene-2,3-dicarboxy Imido, N-[(camphorsulfonyl) oxy] -5-norbornene-2,3-dicarboximide, N-[(perfluorobenzenesulfonyl) oxy] -5-norbornene-2,3-dicarboximide, N- [(P-toluenesulfonate sulfonyl) oxy] -5-norbornene -2,3-dicarboximide, phthalimide triflate, phthalimide perfluorobutane sulfonate, phthalimide perfluorooctane sulfonate, phthalimide o-trifluoromethylbenzene sulfonate, phthalimide camphor sulfonate, phthalimide perfluorobenzene sulfonate, phthalimide p-toluene sulfonate, Diphenyl-iodonium triflate, diphenyl-iodonium perfluorobutane sulfonate, diphenyl-iodonium perfluorooctane sulfonate, diphenyl-iodonium o-trifluoromethylbenzene sulfonate, diphenyl-iodonium camphor sulfonate, diphenyl-iodonium perfluorobenzene sulfonate, diphenyl-iodo Ni p-toluenesulfonate. US Pat. No. 6,803,169 describes a combination of the use of various PAGs.

  In some embodiments of the invention, the PAG is active at a wavelength of about 193 nm or shorter. In some embodiments, the PAG is active at a wavelength of about 193 nm. In some embodiments, the PAG is active at a wavelength of about 13.5 nm.

<Synthesis>
In general, the compounds themselves or compounds for use according to embodiments of the present invention are readily available, for example, by the methods shown in the general reaction schemes as described below, or variations thereof. Can be prepared using available starting materials, reagents and conventional synthetic procedures. In these reactions, variations known per se can be used, but are not described herein.

Any R groups shown in the following reaction schemes and examples are consistent within the scope of the reaction schemes and examples and do not reflect the scope of the R groups elsewhere in this disclosure. .

  Aldol reaction: Hydroxy ketone (3a-e) was produced by the following method. Hemiacetal (2a, 2e) and 2 equivalents of ketone (1a-c) were mixed and stirred for 10 minutes. 0.1 equivalent of piperidine was then added and stirred overnight at room temperature. The solution was then washed with brine and then with water and distilled to produce a pale yellow clear liquid.

  5,5,5-trifluoro-4-hydroxy-4- (trifluoromethyl) -2-pentanone (3f): high pressure reaction of acetone (1a) (58 g, 1 mol) and sulfuric acid (0.58 g, 5.9 mmol) Added to the vessel. The reactor was placed in a dry ice bath and hexafluoroacetone (2f) (182.6 g, 1.1 mol) was added. The reactor was then heated to 70 ° C. in an oil bath and stirred for 18 hours. 3f was separated by distillation under reduced pressure (boiling point: 85-87 ° C., 10 torr). 168 g (75%, yield) of compound 3f was obtained, and the degree of purification was 99.6%.

  Protection: The protected compounds (4a-f) were produced by the following method. Two equivalents of 1,3-propanediol, β-hydroxyketone (3a-f) in toluene and a catalytic amount of pyridinium p-toluenesulfonate were refluxed overnight. The solution was then washed with brine then water and the solvent removed by evaporation to give a clear solid.

Amidation Part 1:

  The amide compound (8a-q, 9a, b) is produced by the following method. Sultone (5, 6) is reacted in diisopropyl ether with 2 equivalents of amine (7a-q) at −20 ° C. for 2 hours. The reaction mixture was dissolved in ethyl acetate and quenched with 5% hydrochloric acid and then saturated sodium bicarbonate. Next, the solution is washed with water, and the solvent is removed by an evaporator to obtain a white solid. The solid is washed with n-hexane, then filtered and dried under vacuum conditions.

Amidation Part 2:

  The amide compound (11a-h, 12) is produced by the following method. Under nitrogen conditions at −20 ° C., 1.05 equivalents of amine salt (10a-h) in diisopropyl ether and acetonitrile, triethylamine was slowly added to keep the reaction temperature at −20 ° C., and then sultone ( 5,6) is added dropwise to the solution. The reaction temperature is maintained at −20 ° C. or lower for 2 hours. The reaction mixture is dissolved in ethyl acetate and quenched with 5% hydrochloric acid, then saturated sodium bicarbonate, and water. The solvent is removed with an evaporator to give a white to pale yellow solid. The solid is washed with n-hexane, then filtered and dried under vacuum conditions.

Esterification:

The ester compound (14a, b 15a, b) is produced by the following method. Sultone (5,6) is reacted with 1.05 equivalents of alcohol (13a, b) in diisopropyl ether at -20 ° C for 2 hours. The reaction mixture is dissolved in ethyl acetate and quenched with 5% hydrochloric acid, saturated sodium bicarbonate, then water. The solvent is removed by an evaporator to obtain a colorless liquid.

1,1-difluoro-2- (2-fluoroacryl) ethanechlorosulfonic acid (18): 2-Fluoroacryloyl chloride is added dropwise to a solution of alcohol (16) in acetonitrile at room temperature for 2 hours. The reaction mixture is dissolved in ethyl acetate and washed with water. The aqueous phase is extracted with ethyl acetate and then the combined organic phases are dried over sodium sulfate. In order to obtain a colorless liquid (17), the solvent is removed with an evaporator. Compound (17) is reacted with 2.0 equivalents of PCl ₅ at 110 ° C. for 1 hour. Distill the reaction mixture under reduced pressure to obtain pure compound (18).

1,1-difluoro-2- (2-fluoroacryl) ethanechlorosulfonic acid (21): In acetonitrile, in the presence of 2.1 equivalents of pyridine, alcohol (16) was converted to 1.05 equivalents of methanesulfonyl chloride. The reaction is allowed to proceed for 2 hours at room temperature and then vinyl chloride is added dropwise to the solution. The reaction mixture is dissolved in ethyl acetate and quenched with 5% hydrochloric acid and then water. The aqueous phase is extracted with ethyl acetate and then the combined organic phases are dried over sodium sulfate. The solvent is removed with an evaporator to obtain a colorless liquid (20). Compound (20) is reacted with 2.0 equivalents of PCL ₅ at 110 ° C. for 1 hour. The reaction mixture is distilled under reduced pressure to give pure compound (21).

  AA: An acid amplifier is produced by the following method. The protected compound (4a-f) is dissolved in diisopropyl ether and 1.05 equivalents of LDA (lithium diisopropylamide) is added dropwise to maintain -20 ° C under nitrogen conditions. The reaction temperature is maintained at −10 ° C. for 1 hour. The reaction mixture is slowly warmed to room temperature and held for 1 hour. Ethanesulfonate unit (8a-q, 9a, b, 11a-h, 12,14a, b, 15a, b18,21) 1.1 equivalent is dissolved in tetrahydrofuran and kept at −20 ° C. under nitrogen condition to protect compound / LDA solution is added dropwise to the ethanesulfonic acid unit solution. The reaction temperature is maintained at 10 ° C. or lower for 1 hour. The reaction mixture is dissolved in ethyl acetate and quenched with water with 5% hydrochloric acid and then saturated sodium bicarbonate and then washed three times with water. Evaporate the solvent to half the amount of the organic phase and place in a cooling bath to obtain a white solid. The solid is washed with diisoproyl ether, then filtered and dried under vacuum conditions.

The table below shows a list of combinations for the synthesis of acid amplifiers using the above compound symbols.

  Alternative synthesis: The synthesis described above is also carried out in a manner analogous to the following examples. The compound numbers in the following examples are not the same as those used in the synthetic reaction schemes and tables above.

Example 1: Preparation of 2- (1-adamantanemethylamino) -1,1-difluoro-2-oxoethanesulfonyl fluoride (3)
1-adamantanemethylamine (2) (0.80 g, 4.84 mmol), pyridine (0.40 g, 5.08 mmol), and CH ₂ Cl ₂ (10 mL) were placed in a nitrogen purged round bottom flask. 2,2-Difluorosulfonylacetylacetyl (1) (0.87 g, 4.84 mmol) dissolved in THF (5 mL) was added dropwise to the flask at 0 ° C. and the solution was stirred for 2 hours. The reaction mixture was diluted with ethyl acetate (20 mL) and washed with 1M HCl (20 mL), saturated aqueous NaHCO ₃ (20 mL) and brine (20 mL). The organics were dried over Na ₂ SO ₄ and the solvent was condensed under reduced pressure. The crude product was purified by column chromatography in hexane with ethyl acetate and acetone to give product (3) (1.38 g). ¹ HNMR (400 MHz, acetone) δ 3.10 (d, J = 6.6, 2H), 1.96 (s, 3H), 1.69 (dd, J = 33.0, 12.2, 6H), 1.55 (d, J = 2.3, 6H).

Example 2: 1,1,1-trifluoro-3- (2-methyl-1,3-dioxan-2-yl) propan-2-yl 2- (1-adamantanemethylamino) -1,1- Preparation of difluoro-2-oxoethanesulfonate >>
1,1,1-trifluoro-3- (2-methyl-1,3-dioxan-2-yl) propan-2-ol (4) (0.346 g, 1.614 mmol) and THF (3 mL) were added. To a 50 mL two-necked flask purged with nitrogen. The flask was cooled to -78 ° C. 1M-hexamethyldisilazide lithium (LiHMDS) dissolved in THF (2.0 mL, 2.03 mmol) was added dropwise to the flask and stirred at −78 ° C. for 20 minutes. 2- (1-adamantanemethylamino) -1,1-difluoro-2-oxoethanesulfonyl fluoride (3) (0.500 g, 1.536 mmol) dissolved in THF (3.0 mL) was added dropwise to the flask, Stir for 24 hours, during which time the solution reached room temperature. The reaction mixture was quenched with 1M HCl (10 mL) and diluted with ethyl acetate (30 mL). The organic phase was washed with saturated aqueous NaHCO ₃ (15 mL) and brine (15 mL). The organic layer was then dried over Na ₂ SO ₄ and the solvent was condensed under reduced pressure. The crude product was purified by column chromatography with ethyl acetate in hexanes to give product (5) (0.467 g). ¹ HNMR (400 MHz, acetone) δ 5.74-5.62 (m, 1H), 4.15-3.97 (m, 2H), 3.92-3.74 (m, 2H), 3.08- 3.00 (m, 2H), 2.32-1.11 (m, 2H), 2.11-1.99 (m, 1H), 1.97 (d, J = 9.8, 3H), 1.77-1.60 (dd, J = 32.0, 12.0, 6H), 1.59-1.50 (s, 9H), 1.44-1.36 (m, 1H).

Example 3 Preparation of (1-adamantanemethyl) -2,2-difluoro-2- (fluorosulfonyl) acetate (7)
1-adamantane methyl alcohol (6) (3.32 g, 19.9 mmol), pyridine (1.65 g, 20.89 mmol), and CH ₂ Cl ₂ (20 mL) were placed in a nitrogen purged round bottom flask. 2,2-Difluorosulfonylacetyl fluoride (1) (3.60 g, 19.9 mmol) dissolved in THF (10 mL) was added dropwise to the flask at 0 ° C. and the solution was stirred for 2 hours. The reaction mixture was diluted with ethyl acetate (30 mL) and washed with 1M HCl (20 mL), saturated aqueous NaHCO ₃ (20 mL), and brine (20 mL). The organic phase was dried over Na ₂ SO ₄ and the solvent was condensed under reduced pressure. The crude product was purified by column chromatography in hexane with ethyl acetate and acetone to give product (7) (4.83 g). ¹ HNMR (400 MHz, Acetone) δ 4.05 (s, 2H), 2.03 (s, 3H), 1.71 (dd, J = 37.3, 11.9, 6H), 1.57 (d, J = 2.4, 6H).

Example 4: (1-adamantanemethyl) -2,2-difluoro-2- [1,1,1-trifluoro-3- (2-methyl-1,3-dioxan-2-yl) propane-2 -Preparation of -yloxysulfonyl] acetate (8) >>
1,1,1-trifluoro-3- (2-methyl-1,3-dioxan-2-yl) propan-2-ol (4) (0.394 g, 1.839 mmol) and THF (3 mL) were added. To a 50 mL two-necked flask purged with nitrogen. The flask was cooled to -78 ° C. 1M-hexamethyldisilazide lithium (LiHMDS) dissolved in THF (2.2 mL, 2.20 mmol) was added dropwise to the flask and stirred at −78 ° C. for 20 minutes. (1-adamantanemethyl) -2,2-difluoro-2- (fluorosulfonyl) acetate (7) (0.600 g, 1.839 mmol) dissolved in THF (3 mL) was added dropwise to the flask and stirred for 24 hours. During this time, the solution reached room temperature. The reaction mixture was quenched with 1M HCl (10 mL) and diluted with ethyl acetate (30 mL). The organic phase was washed with saturated aqueous NaHCO ₃ (15 mL) and brine (15 mL). The organic phase was then dried over Na ₂ SO ₄ and the solvent was condensed under reduced pressure. The crude product was purified by column chromatography with ethyl acetate in hexanes to give product (8) (0.543 g). ¹ HNMR (400 MHz, DMSO) δ 5.76-5.62 (m, 1H), 4.02 (d, J = 4.0, 2H), 4.00-3.90 (m, 2H), 3. 85-3.61 (m, 2H), 2.32-2.09 (m, 2H), 2.00 (s, 3H), 1.91-1.78 (m, 1H), 1.73- 1.56 (dd, J = 36.0, 11.9, 6H), 1.53 (d, J = 1.2, 6H), 1.50-1.41 (s, 3H), 1.42 (D, J = 4.3, 1H).

Example 5: 1,1,1-trifluoro-3- (2-phenyl-1,3-dioxolan-2-yl) propan-2-yl-1,1-difluoro-2-oxo-2- ( Preparation of phenylamino) ethanesulfonate (11) >>
1,1,1-trifluoro-3- (2-phenyl-1,3-dioxolan-2-yl) propan-2-ol (10) (0.913 g, 3.482 mmol) and THF (3 mL) were added. To a 50 mL two-necked flask purged with nitrogen. The flask was cooled to -78 ° C. 1M-hexamethyldisilazide lithium (LiHMDS) dissolved in THF (4.2 mL, 4.179 mmol) was added dropwise to the flask and stirred at −78 ° C. for 20 minutes. 1,1-Difluoro-2-oxo-2- (phenylamino) ethanesulfonyl fluoride (9) (0.881 g, 3.483 mmol) dissolved in THF (5 mL) was added dropwise to the flask and stirred for 24 hours. In the meantime, the solution reached room temperature. The reaction mixture was quenched with 1M HCl (10 mL) and diluted with ethyl acetate (30 mL). The organic phase was washed with saturated aqueous NaHCO ₃ (15 mL) and brine (15 mL). The organic phase was then dried over Na ₂ SO ₄ and the solvent was condensed under reduced pressure. The crude product was purified by column chromatography with ethyl acetate in hexanes to give product (11) (0.625 g). ¹ HNMR (400 MHz, acetone) δ 7.79 (d, J = 7.9, 2H), 7.47-7.33 (m, 7H), 7.26 (t, J = 7.4, 1H), 5.66-5.44 (m, 1H), 4.21-4.06 (m, 2H), 3.85-3.63 (m, 2H), 2.67-2.44 (m, 2H) ).

Example 6 1,1-Difluoro-3- (2-phenyl-1,3-dioxolan-2-yl) propan-2-yl-1,1-difluoro-2-oxo-2- (phenylamino) Preparation of ethanesulfonate (13) >>
1,1-difluoro-3- (2-phenyl-1,3-dioxolan-2-yl) propan-2-ol (12) and THF were added to a nitrogen purged flask. The flask was cooled to -78 ° C. 1M-hexamethyldisilazide lithium (LiHMDS) dissolved in THF was added dropwise to the flask and stirred at -78 ° C. for 20 minutes. 1,1-Difluoro-2-oxo-2- (phenylamino) ethanesulfonyl fluoride (9) dissolved in THF was added dropwise to the flask and stirred for 24 hours, during which time the solution reached room temperature. The reaction mixture was quenched with 1M HCl and diluted with ethyl acetate. The organic phase was washed with a saturated aqueous NaHCO ₃ solution and brine. The organic phase was then dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by column chromatography with ethyl acetate in hexane to give product (13).

Example 7: 1,1-Difluoro-3- (2-methyl-1,3-dioxan-2-yl) propan-2-yl-1,1-difluoro-2-oxo-2- (phenylamino) Preparation of ethanesulfonate (15) »
1,1-Difluoro-3- (2-methyl-1,3-dioxan-2-yl) propan-2-ol (14) and THF were added to a nitrogen purged flask. The flask was cooled to -78 ° C. 1M-hexamethyldisilazide lithium (LiHMDS) dissolved in THF was added dropwise to the flask and stirred at -78 ° C. for 20 minutes. 1,1-Difluoro-2-oxo-2- (phenylamino) ethanesulfonyl fluoride (9) dissolved in THF was added dropwise to the flask and stirred for 24 hours, during which time the solution reached room temperature. The reaction mixture was quenched with 1M HCl and diluted with ethyl acetate. The organic phase was washed with a saturated aqueous NaHCO ₃ solution and brine. The organic phase was then dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by column chromatography with ethyl acetate in hexane to give product (15).

Example 8: 4,4,4-trifluoro-1- (2-methyl-1,3-dioxan-2-yl) butan-2-yl-1,1-difluoro-2-oxo-2- ( Preparation of phenylamino) ethanesulfonate (17) >>
4,4,4-Trifluoro- (2-methyl-1,3-dioxan-2-yl) butan-2-ol (16) and THF were added to a nitrogen purged flask. The flask was cooled to -78 ° C. 1M-hexamethyldisilazide lithium (LiHMDS) dissolved in THF was added dropwise to the flask and stirred at -78 ° C. for 20 minutes. 1,1-Difluoro-2-oxo-2- (phenylamino) ethanesulfonyl fluoride (9) dissolved in THF was added dropwise to the flask and stirred for 24 hours, during which time the solution reached room temperature. The reaction mixture was quenched with 1M HCl and diluted with ethyl acetate. The organic phase was washed with a saturated aqueous NaHCO ₃ solution and brine. The organic phase was then dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by column chromatography with ethyl acetate in hexane to give product (17).

Example 9: Preparation of 1,1,1-trifluoro-5-hydroxy-5-methylhexane-3-yl 1,1-difluoro-2-oxo-2- (phenylamino) ethanesulfonate
6,6,6-trifluoro-2-methylhexane-2,4-diol (18) and THF were added to a nitrogen purged flask. The flask was cooled to -78 ° C. 1M-hexamethyldisilazide lithium (LiHMDS) dissolved in THF was added dropwise to the flask and stirred at -78 ° C. for 20 minutes. 1,1-Difluoro-2-oxo-2- (phenylamino) ethanesulfonyl fluoride (9) dissolved in THF was added dropwise to the flask and stirred for 24 hours, during which time the solution reached room temperature. The reaction mixture was quenched with 1M HCl and diluted with ethyl acetate. The organic phase was washed with a saturated aqueous NaHCO ₃ solution and brine. The organic phase was then dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The crude product was purified by column chromatography with ethyl acetate in hexane to give the product (19).

Synthesis of polymer-bound acid amplifying agents

A general methodology for the preparation of polymer ketal-triggered acid amplifiers and polymer chains useful for EUV lithography is shown below.

One specific example of such polymer synthesis is described below.

Hydroxystyrene, styrene, 2-methyl-2-adamantyl methacrylic resin, 2- (2,2-difluoro-2- (1,1,1-trifluoro-3- (2-methyl-1,3dioxane-2- Yl) propan-2-yloxysulfonyl) acetamido) ethyl methacrylic resin (acid amplifier monomer), NaHCO ₃ , and THF were added to a two-necked flask and degassed with nitrogen for 15 minutes. A radical initiator 2,2′-azobis- (2-methylbutyronitrile) (AIBN) was weighed in a flask and dissolved in THF. The AIBN solution was added to the monomer solution and the reaction mixture was refluxed for 24 hours. After refluxing overnight, the THF was removed under reduced pressure and the remaining polymer was dissolved in MeOH. The polymer solution was poured into a beaker containing water. The precipitated polymer was filtered and dried to give the desired product.

"result"
Table I compares the ratio of uncatalyzed rate constant (k _base ) and autocatalytic / uncatalyzed (no k _base / k _base ) rate constant for several active generation 2 and generation 3AAs. Among Generation 2, 3HF has the best k- _{no base} / k _base ratio (at 100 ° C.) 1390 and 3HG has a k _base-free / k _base ratio (at 100 ° C.) 300, which is pentafluorobenzenesulfonic acid generating a is the best ratio among the AAs, 11HG is the most thermally stable AA to produce a pentafluorobenzenesulfonic acid has a k _{base without} / k _base ratio (at 100 ° C.) 1.0 . 6AB is also Generation 2AA and has the best thermal stability at 100 ° C. and 145 ° C. with k _{bases of} 0.49 × 10 ⁻⁵ s ⁻¹ and 13 × 10 ⁻⁵ s ⁻¹ respectively. The k _baseless / k _base ratio is 490 and 270 at 100 ° C. and 145 ° C., respectively. The high thermal stability and moderate k _base-free / k _base ratio is to some extent due to the relatively low fluorinated sulfonic acid precursor 4- (trifluoromethyl) benzenesulfonate. In comparison, both Generation 3AAs have a k _base and a k _base / k _base ratio far superior to the best generation 2 AAs. 29OC and 29OG have k _bases 0.43 × 10 ⁻⁵ s ⁻¹ and 0.009 × 10 ⁻⁵ s ⁻¹ at 145 ° C., respectively. Even if they generate strong fluorinated sulfonic acid, pentafluorobenzene sulfonic acid and triflic acid, they are 30 and 1400 times more stable than 6AB. 29OC and 29OG also have unprecedented k _base / k _base ratios of 28,000 and 1,000,000, respectively. With such promising results, Generation 3AAs provide an opportunity to create AAs with various properties.

  Formulation: All resists are composed of 3% by weight solids and a 95/5 mixture of propylene glycol methyl ether acetate and ethyl lactate. The resist solid is 8% by weight of di (4-tert-butylphenyl) iodonium perfluoro-1-butane-sulfonic acid photoacid generator (PAG), 1.5% by weight of tetrabutylammonium hydroxide base, and 1 mol%. And the remaining solid of 4-hydroxystyrene / styrene / 2-methyl-2-adamantylmethacrylic acid (60/20/20) polymer. FIG. 1 shows the formulation and process parameters changed for each of the four resists (KH-2, KH-14, KH-25 and KH-23).

  Process: FIG. 2 shows 40 nm L / S imaging results of four resists each containing three acid amplifiers and one control at three different post-exposure baking (PEB) temperatures. The resist film is covered to a thickness of 60 nm by a rotation speed (FIG. 1) and soft baking at 130 ° C. for 120 seconds. The film is exposed to EUV radiation on an Albany Micro Exposure Tool (AMET) with annular illumination, post-exposure at 100 ° C., 110 ° C. or 120 ° C. for 90 seconds, and in 0.26N tetramethylammonium hydroxide for 45 seconds. Developed. Overall, all three acid amplifiers improved the sensitivity of the control resist. KH-25 slightly improved sensitivity at line edge roughness (LER) and at each of the three simultaneously tested PEB temperatures. Both KH-14 and KH-23 improved sensitivity twice as much as the control without causing a significant change in LER. The exposure results show that each of these acid amplifiers improves sensitivity with little impact on LER in most cases.

  One skilled in the art will appreciate that variations can be used to obtain ethers, amines, thiols, thiol esters, etc., rather than the indicated alcohol or acetate. It will also be appreciated that the alcohol can be esterified with a polymer, such as a photoresist polymer. In some cases, it is expected to provide the resist with a higher concentration of acid amplifier than would otherwise be achievable without significantly degrading other resist properties. Furthermore, depending on the choice of acid amplifying agent, binding to the polymer can be used to affect the solubility of the polymer, ie, create a “solubility switch”.

  Although the invention has been described in detail with particular reference to certain embodiments of the invention, those skilled in the art will recognize that variations and modifications can be made within the spirit and scope of the invention.

Claims (38)

Formula I:
{In the formula, G ¹ represents -N ⁺ (CH ₃ ) ₃ ,-(CH ₂ ) -N ⁺ (CH ₃ ) ₃ ,-(CH ₂ ) -NO ₂ , -CH ₂ (CN), -CH ( CN) ₂ , — (CH ₂ ) _0-1 SO ₂ (C ₁ -C ₈ ) hydrocarbon group, —C ₆ F ₅ , —Si (CH ₃ ) ₃ , halogen atom, —C _i H _j (halogen atom) ) _K , and —C _s H _t (halogen atom) _u —E, wherein i is 1-2, j is 0-3, k is 1-5, and j the sum of k is 2i + 1; and s is 1-2, t is 0-2, u is 1-4, and the sum of t and u is 2s;
E is, - _(C 1 -C ₆₎ alkyl group, an aryl _{group, (C} 1 -C ₆₎ haloalkyl group, a haloaryl group, haloaryl _(C 1 -C ₂₎ alkyl group, and aryl _(C 1 _-C 2) Selected from alkyl groups;
G ² is selected from a hydrogen atom, —CF ₃ , —N ⁺ (CH ₃ ) ₃ , a halogen atom, and a (C ₁ -C ₁₀ ) hydrocarbon group;
AA is the following part:
a)
[In the formula, M, -O -, - S-, or ^{-NR 90} - and is;
R ¹⁰ is a (C ₁ -C ₈ ) saturated hydrocarbon group; a (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group or a nitro group; (C ₁ -C ₈ ) a silaalkane group; -O- _(C 1 -C ₈₎ saturated hydrocarbon group; a halogen atom, a cyano group or -O- substituted by nitro group _(C 1 -C ₈₎ saturated hydrocarbon group; -S- _(C 1 -C ₈ ) a saturated hydrocarbon group; a —S— (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group or a nitro group; and an optionally substituted phenyl group; Selected R ²⁰ is selected from a hydrogen atom, a (C ₁ -C ₆ ) hydrocarbon group and a nitro group, a cyano group or a substituted (C ₁ -C ₆ ) hydrocarbon group, or a combination thereof. R ¹⁰ and R, together with carbon ²⁰ forms a 3-8 membered ring;
R ⁴⁰ is a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a —C (═O) (C ₁ -C ₆ ) alkyl group, a —C (═O) (C ₁ -C ₆ ) alkenyl group, — C (═O) (C ₁ -C ₆ ) haloalkyl group, benzyl group, substituted benzyl group, —C (═O) phenyl group, substituted —C (═O) phenyl group, —SO ₂ phenyl group Or —SO ₂ (substituted) phenyl group; or when M is O or S, both R ¹⁰ and R ⁴⁰ are optionally one or more (C ₁ — C ₆ ) can form 4- to 8-membered rings that may be substituted with hydrocarbon groups;
R ⁵⁰ is a hydrogen atom, a (C ₁ -C ₆ ) hydrocarbon group, a nitro group, a cyano group, a nitro group or a (C ₁ -C ₆ ) hydrocarbon group substituted with a cyano group, and (C ₁ -C ₆ ) selected from silaalkane groups, or together with the carbon to which they are attached, R ¹⁰ and R ^{50 form} a (C ₃ -C ₈ ) hydrocarbon ring; or When O or S, R ²⁰ and R ⁵⁰ can together form a 3-8 membered ring optionally substituted with one or more (C ₁ -C ₆ ) hydrocarbon groups;
R ⁹⁰ is selected from a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a —C (═O) (C ₁ -C ₆ ) alkyl group and a phenyl group, or a nitrogen to which they are bonded; Together, provided that one of R ⁴⁰ and R ⁹⁰ must be an acyl group, R ⁴⁰ and R ⁹⁰ can form a nitrogen heterocycle and the nitrogen to which they are attached. And when R ⁴⁰ and R ⁹⁰ form a heterocycle, the heterocycle shall contain 1 or 2 α-oxo substituents]; and b)
Wherein R ^W , R ^X and R ^y are each independently selected from a hydrogen atom, a (C ₁ -C ₁₀ ) hydrocarbon group and a (C ₁ -C ₈ ) silaalkane group;
R ¹⁰⁰ is selected from a hydrogen atom and a (C ₁ -C ₂₀ ) hydrocarbon group; or any ^two of R ¹⁰⁰ , R ^W , R ^X , R ^y and G ² are attached to each other Together with the formed carbon to form a (C ₅ -C ₈ ) hydrocarbon ring which may be substituted with a (C ₁ -C ₈ ) hydrocarbon group, provided that the C═C double bond is C) G ¹ and AA together with the carbon to which they are attached, together with the non-aromatic 5- or 6-membered ring D:
Wherein R ^g is independently selected in each case from a hydrogen atom, —M—R ⁴⁰ , (C ₁ -C ₁₀ ) hydrocarbon group, hydroxyl group, and R ^h CH ₂ COO—. Wherein R ^h is selected from a halogen atom and a hydroxyl group; G ³ is —N ⁺ (CH ₃ ) ₂ , — (CH) —NO ₂ , —CH (CN) _{), - C (CN) 2} , -Si (CH 3) 2 -, - C i H j ( selected from halogen _{atoms) k,} and _C s _{H t} (halogen _atoms) u -E, where i is 1 -2, j is 0-3, k is 1-5, and the sum of j and k is 2i; further, s is 1-2, t is 0-2 There, u is 1 to 4, and the sum of t and u is located at 2s-1; ^{R a} and ^{R B} in the formula each independently Hydrogen _{atom, (C} 1 -C ₆₎ may be selected from alkyl and benzyl group,]
Can form
AB is selected from F and CF ₃ ;
AC represents —C (═O) NR ^AC —, —C (═O) O—, —CH ₂ O—, —CH ₂ OC (═O) —, and —CH ₂ OC (═O) NR ^AC —. Wherein R ^AC is selected from a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, and a phenyl group;
AD is a direct _{^{bond, - (CR AD R AD)}} m (O) -, - (CR AD R AD) m (O) n (C = O) -, - (CR AD R AD) m (NR AD) _{n (C = O) p -} , - AE (O) n (C = O) p -, and _{^{-AE (NR AD) n (C}} = O) p - is selected from;
m is 0, 1, 2, 3 or 4;
n is 0 or 1;
p is 0 or 1;
R ^AD can be independently selected from a hydrogen atom and a (C ₁ -C ₆ ) alkyl group;
AE is
Is;
R ⁷² was independently selected in each case from a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, a — (C ₁ -C ₄ ) haloalkyl group, —NO ₂ , F, Br, and Cl. Represents 1 to 4 substituents;
AF is the next part:
_{a) -C (= CH 2)} AG;
b) -C _a H _b F _{c wherein} a is 1-15, b is 0-30, c is 1-31, and the sum of b and c is 2a + 1;
c)-(R ^d ) or -C _A H _B (R ^d ) _{D wherein} A is selected from 1, 2, 3, and 4 and B is selected from an integer between 0 and 1-9 , D is selected from 1, 2 and 3, and the sum of B and D is 2A + 1; R ^d is in each case selected from hydrogen and a (C ₃ -C ₁₂ ) alicyclic hydrocarbon group; Said (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group can optionally be substituted with one or more substituents selected from R ⁶¹ and R ⁷¹ ; and R in the formula as at least one example of ^d _is (C 3 _{-C 12)} aliphatic cyclic hydrocarbon group];
d)
e)
Selected from
AG is selected in each case from a hydrogen atom, F, CH ₃ , and CF ₃ ;
R ⁶¹ represents a hydrogen atom, —OH, —CF ₃ , — (C ₁ -C ₄ ) alkyl group, —OCH ₃ , —C (═O) OR ^AD , —OC (═O) R ^AD , —C ( = ^{O) R AD,} a cyano _{group, -NO 2, F, Cl,} Br, -CH 2 Br, -CH = CH 2, -OCH 2 CH 2 Br, -OC = OCH = CH 2, and -OC = OCCH It is selected from ₃ = CH _2;
R ⁷¹ is, in each case, a hydrogen atom, —CF ₃ , —OH, —OCH ₃ , —C═O (oxo), — (C ₁ -C ₄ ) alkyl group, —NO ₂ , F, Br, It represents Cl, _-C i _{H j} (halogen _{atoms) k} and _C s _{H t} 1 to 4 substituents independently selected from (a halogen _atom) u -E, wherein, i is located at 1-2 , J is 0-3, k is 1-5, and the sum of j and k is 2i + 1; and s is 1-2, t is 0-2, u is 1 to 4 and the sum of t and u is 2s;
E is, - _(C 1 -C ₆₎ alkyl group, an aryl _{group, (C} 1 -C ₆₎ haloalkyl group, a haloaryl group, haloaryl _(C 1 -C ₂₎ alkyl group, and aryl _(C 1 _-C 2) Selected from alkyl groups; and when AB is not F and AC is —CH ₂ OC (═O) —, AF shall not be —CCH ₃ ═CH ₂ or —CH═CH ₂ ;
When AB is F, AC is -C (= O) NH-, and AD is a direct bond (when m, n, and p are each 0), AF is not a substituted benzene age;
The compound represented by the formula (I) is 2,2,2-trifluoro-1- (6,10-dioxaspiro [4.5] decan-1-yl) ethyl 1,1-difluoro-2-oxo. -2- (phenylamino) ethanesulfonic acid,
1,1,1-trifluoro-4-methylpent-4-en-2-yl 1,1-difluoro-2-oxo-2- (phenylamino) ethanesulfonate, or 1,1,1-trifluoro-3 -(2-Methyl-1,3-dioxan-2-yl) propan-2-yl1,1-difluoro-2-oxo-2- (phenylamino) ethanesulfonate}
A compound represented by Formula II:
{In the formula, G ¹ represents -N ⁺ (CH ₃ ) ₃ ,-(CH ₂ ) -N ⁺ (CH ₃ ) ₃ ,-(CH ₂ ) -NO ₂ ,-(CH ₂ ) (CN),- (CH) (CN) ₂ , — (CH ₂ ) _0-1 SO ₂ (C ₁ -C ₈ ) hydrocarbon group, —C ₆ F ₅ , —Si (CH ₃ ) ₃ , halogen atom, —C _i H _j (halogen atom) _k and -C _s H _t (halogen atom) _u -E, wherein i is 1-2, j is 0-3, and k is 1-5. And the sum of j and k is 2i + 1; s is 1-2, t is 0-2, u is 1-4, and the sum of t and u is 2s;
E is, - _(C 1 -C ₆₎ alkyl group, an aryl _{group, (C} 1 -C ₆₎ haloalkyl group, a haloaryl group, haloaryl _(C 1 -C ₂₎ alkyl group, and aryl _(C 1 _-C 2) Selected from alkyl groups;
G ² is selected from a hydrogen atom, —CF ₃ , —N ⁺ (CH ₃ ) ₃ , a halogen atom, and a (C ₁ -C ₁₀ ) hydrocarbon group;
AA is the following part:
a)
Wherein M is —O—, —S—, or —NR ⁹⁰ —;
R ¹⁰ is a (C ₁ -C ₈ ) saturated hydrocarbon group; a (C ₁ -C ₈ ) saturated hydrocarbon group substituted with a halogen atom, a cyano group, or a nitro group; (C ₁ -C ₈ ) a silaalkane group ; -O- _(C 1 -C ₈₎ saturated hydrocarbon group; a halogen atom, a cyano group, or -O- substituted with nitro group _(C 1 -C ₈₎ saturated hydrocarbon group; -S- _{(C 1} phenyl and, where optionally a be substituted; -C ₈₎ saturated hydrocarbon group; a halogen atom, a cyano group, or -S- substituted with nitro group (C 1 _{-C 8)} saturated hydrocarbon group R ²⁰ is selected from a hydrogen atom, a (C ₁ -C ₆ ) hydrocarbon group, and a nitro group, a cyano group or a substituted (C ₁ -C ₆ ) hydrocarbon group, or Together with the carbons to which they are attached, R ¹⁰ and R ²⁰ are 3 Forms a ~ 8 membered ring;
R ^40a is a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a —C (═O) (C ₁ -C ₆ ) alkyl group, a —C (═O) (C ₁ -C ₆ ) alkenyl group, — C (═O) (C ₁ -C ₆ ) haloalkyl group, benzyl group, substituted benzyl group, —C (═O) phenyl group, substituted —C (═O) phenyl group, —SO ₂ phenyl group, — Or selected from SO ₂ (substituted) phenyl group and Q; or when M is O or S, both R ¹⁰ and R ^40a are optionally one or more (C ₁ -C ₆ ). Can form a 4-8 membered ring which may be substituted with a hydrocarbon group;
R ⁵⁰ represents a hydrogen atom, a (C ₁ -C ₆ ) hydrocarbon group, a nitro group, a cyano group, a cyano group or a (C ₁ -C ₆ ) hydrocarbon group substituted with a nitro group, and (C ₁ -C ₆ ) selected from silaalkane groups or together with the carbon to which they are attached, R ¹⁰ and R ^{50 form} a (C ₃ -C ₈ ) hydrocarbon ring; or M is O Or, when S, R ²⁰ and R ⁵⁰ together may form a 3- to 8-membered ring which may be optionally substituted with one or more (C ₁ -C ₆ ) hydrocarbon groups. Can;
R ⁹⁰ is selected from a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a —C (═O) (C ₁ -C ₆ ) alkyl group and a phenyl group, or a nitrogen to which they are bonded; Together, provided that one of R ^40a and R ⁹⁰ must be an acyl group, R ^40a and R ⁹⁰ can form a nitrogen heterocycle and the nitrogen to which they are attached. When R ^40a and R ⁹⁰ together form a heterocycle, the heterocycle shall contain 1 or 2 α-oxo substituents]; and b)
[Wherein R ^W , R ^X and R ^y are each independently selected from a hydrogen atom, a (C ₁ -C ₁₀ ) hydrocarbon group and a (C ₁ -C ₈ ) silaalkane group;
R ¹⁰⁰ is selected from a hydrogen atom and a (C ₁ -C ₂₀ ) hydrocarbon group; or any ^two of R ¹⁰⁰ , R ^W , R ^X , R ^y and G ² are attached to them. Together with carbon, it forms a (C ₅ -C ₈ ) hydrocarbon ring optionally substituted with a (C ₁ -C ₈ ) hydrocarbon group, provided that the C═C double bond is Not included in the phenyl ring]; or c) G ¹ and AA together with the carbon to which they are attached, together with the non-aromatic 5- or 6-membered ring D:
[Wherein R ^g is independently selected from a hydrogen atom, —M—R ^40a , (C ₁ -C ₁₀ ) hydrocarbon group, hydroxyl group, and R ^h CH ₂ COO— in each case. Or represents a substituent of 2, wherein R ^h is selected from a halogen atom, a hydroxyl group, a polymer, and an oligomer; wherein G ³ is —N ⁺ (CH ₃ ) ₂ , — (CH) —NO _{2 , -CH (CN), - C} (CN) 2, -Si (CH 3) 2 -, - C i H j ( halogen _{atom) k,} and is selected from _-C s _{H t} (halogen _atoms) u -E Where i is 1-2, j is 0-3, k is 1-5, and the sum of j and k is 2i; and s is 1-2, t is 0-2, u is 1-4, and the sum of t and u is 2s-1; where R ^A and R ^B can be independently selected from hydrogen, (C ₁ -C ₆ ) alkyl and benzyl groups]
Can form
AB is F and CF ₃ ;
AC represents —C (═O) NR ^AC —, —C (═O) O—, —CH ₂ O—, —CH ₂ OC (═O) —, and —CH ₂ OC (═O) NR ^AC —. Wherein ^RAC is selected from a hydrogen atom, a (C ₁ -C ₆ ) alkyl group and a phenyl group;
AD is a direct _{^{bond, - (CR AD R AD)}} m (O) -, - (CR AD R AD) m (O) n (C = O) -, - (CR AD R AD) m (NR AD) _{n (C = O) p -} , - AE (O) n (C = O) p -, and _{^{-AE (NR AD) n (C}} = O) p - is selected from;
m is 0, 1, 2, 3 or 4;
n is 0 or 1;
p is 0 or 1;
R ^AD can be independently selected from a hydrogen atom and a (C ₁ -C ₆ ) alkyl group;
AE is
Is;
R ⁷² was independently selected in each case from a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, a — (C ₁ -C ₄ ) haloalkyl group, —NO ₂ , F, Br, and Cl. Represents 1 to 4 substituents;
AF ^a is the following part:
_{a) -C (= CH 2)} AG;
b) -C (AG) (Q ) CH 2 Q;
c) -C _a H _b F _c (wherein a is 1 to 15, b is 0 to 30, c is 1 to 31, and the sum of b and c is 2a + 1);
d)-(R ^da ) or -C _A H _B (R ^da ) _D [A is selected from 1, 2, 3 and 4; B is selected from an integer between 0 and 1-9; Is selected from 1, 2 and 3, and the sum of B and D is 2A + 1; R ^da is in each case selected from a hydrogen atom and a (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group, The (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group can be optionally substituted with one or more substituents selected from R ^61a and R ⁷¹ ; and R ^{da in} the formula At least one example of is an optionally substituted (C ₃ -C ₁₂ ) aliphatic cyclic hydrocarbon group];
e)
f)
Selected from
AG is in each case selected from a hydrogen atom, F, CH ₃ and CF ₃ ;
R ^61a is a hydrogen atom, —OH, —CF ₃ , — (C ₁ -C ₄ ) alkyl group, —OCH ₃ , —C (═O) OR ^AD , —OC (═O) R ^AD , —C ( ═O) R ^AD , cyano group, —NO ₂ , F, Cl, Br, —CH ₂ Br, —CH═CH ₂ , —OCH ₂ CH ₂ Br, —Q, —CH ₂ —Q, —O—Q _{, -OCH 2 CH 2 -Q, -OCH} 2 CH 2 O-Q, -CH (Q) CH 2 -Q, -OC = OCH = CH 2, -OC = OCCH 3 = CH 2, -OC = OCHQCH 2 It is selected from Q and -OC = OCCH ₃ QCH ₂ Q;
R ⁷¹ is, in each case, a hydrogen atom, —CF ₃ , —OH, —OCH ₃ , —C═O (oxo), — (C ₁ -C ₄ ) alkyl group, —NO ₂ , F, Br, represents Cl, _-C i _{H j} (halogen _{atoms) k} and _-C s _{H t} 1 to 4 substituents independently selected from (a halogen _atom) u -E, wherein, i is 1-2 And j is 0-3, k is 1-5, and the sum of j and k is 2i + 1; and s is 1-2, t is 0-2, u Is 1 to 4 and the sum of t and u is 2s;
E is, - _(C 1 -C ₆₎ alkyl group, an aryl _{group, (C} 1 -C ₆₎ haloalkyl group, a haloaryl group, haloaryl _(C 1 -C ₂₎ alkyl group, and aryl _(C 1 _-C 2) Selected from alkyl groups; and Q is a polymer or oligomer;
In which at least one of the substituents of the compound must be or must contain Q;
And AF is F and AC is —CH ₂ OC (═O) —, AF ^a is —CCH ₂ QCH ₂ Q, —CHQCH ₂ Q, —CCH ₃ = CH ₂ , or —CH═. Shall not be CH ₂ ; and
When AB is F, AC is —C (═O) NH—, and AD is a direct bond (when m, n, and p are each 0), AF ^a is not a substituted benzene. Shall. }
A compound represented by AA is
The compound according to claim 1 or 2, wherein   4. A compound according to claim 3, wherein M is O. The compound according to claim 4, wherein R ¹⁰ and R ⁴⁰ or R ¹⁰ and R ^40a form a ring. AA has the following parts:
6. A compound according to claim 5 selected from. G ² is selected from hydrogen atoms and -CF _3, A compound according to claim 1 or 2. The compound according to claim 7, wherein G ² is a hydrogen atom. G ¹ _is, -CF 3, are selected from _-CF 2 H, and CH ₂ F, the compound according to claim 1 or 2. AC ^{is, -C (= O) NR AC} -, - C (= O) O-, and _-CH 2 O-, and _-CH 2 OC (= O) - is selected from, in claim 1 or 2 The described compound. AC ^{is, -C (= O) NR AC} - A compound according to claim 10.   12. A compound according to claim 11 wherein AC is -C (= O) NH-. The compound according to claim 10, wherein AC is —CH ₂ OC (═O) —. AC is, _-CH 2 is O-, A compound according to claim 10.   11. A compound according to claim 10, wherein AC is -C (= O) O-. AD is a direct _{^{bond, - (CR AD R AD)}} m (O) -, - (CR AD R AD) m (O) n (C = O) -, and _{-AE (O) n (C =} O) 3. A compound according to claim 1 or 2 selected from _p- . AD is a direct _{^{bond, - (CR AD R AD)}} 2 O (C = O) -, - C (= O), - (CH 2) 2 O-, and
3. A compound according to claim 1 or 2 selected from 18. A compound according to claim 17, wherein R ^AD is in each case selected from a hydrogen atom and a methyl group. AF or AF ^a is-(R ^d ), -C _A H _B (R ^d ) _D ,-(R ^da ), -C _A H _B (R ^da ) _D , -C (= CH ₂ ) AG, and
Wherein R ^d or R ^da can in each case optionally be substituted with one or more substituents selected from R ⁶¹ , R ^61a and R ⁷¹ (C ₃ -C ₁₂₎ is selected from aliphatic cyclic hydrocarbon compound according to claim 1 or 2. AF or AF ^a is selected from R ^d and — (CH ₂ ) R ^d , or R ^da and — (CH ₂ ) R ^da ; and wherein R ^d or R ^da is optionally a hydrogen atom, —OH , — (C ₁ -C ₄ ) alkyl group, —OCH ₃ , —C (═O) O (R ^AD ), —OC (═O) R ^AD , oxo, —C (═O) R ^AD and cyano group 21. The compound of claim 19, which is an adamantyl group that may be substituted with 1 or 2 moieties selected from: The adamantyl group may optionally be a hydrogen atom, —OH, CH ₃ , —OCH ₃ , —C (═O) O (CH ₃ ), —OC (═O) (CH ₃ ), oxo, —C (═O ) CH _3, and a be substituted with 1 or 2 moieties selected from cyano group, a compound according to claim 20. AF or AF ^a is, -C (= _CH 2) is AG, A compound according to claim 19. AF or AF ^a is
The compound according to claim 19. G ² is a hydrogen atom;
The compound of claim 1, wherein M is an oxygen atom; and AC is —C (═O) NH—. AD is a direct _{^{bond, - (CR AD R AD)}} 2 O (C = O) -, - (CH 2) 2 O, and
25. The compound of claim 24, selected from: AF or AF ^a is —C (═CH ₂ ) AG; optionally a phenyl group substituted with R ⁶¹ or R ^61a ; R ^d or R ^da ; and — (CH ₂ ) R ^d or — (CH ₂ ) R ^da ;
Here, R ^d or R ^da is optionally a hydrogen atom, —OH, — (C ₁ -C ₄ ) alkyl group, —OCH ₃ , —C (═O) O (R ^AD ), —OC (= 26. A compound according to claim 24 or 25 which is an adamantyl group which may be substituted with one or two moieties selected from O) ^RAD , oxo, -C (= O) ^RAD and a cyano group. G ² is a hydrogen atom;
M is an oxygen atom;
AC is -C (= O) O-;
AD is a direct bond; and AF or AF ^a is selected from R ^d , R ^da , — (CH ₂ ) R ^d and — (CH ₂ ) R ^da ;
Here, R ^d or R ^da is optionally a hydrogen atom, —OH, — (C ₁ -C ₄ ) alkyl group, —OCH ₃ , —C (═O) O (R ^AD ), —OC (═O) The compound according to claim 1 or 2, which is an adamantyl group which may be substituted with 1 or 2 moieties selected from R ^AD , oxo, -C (= O) R ^AD and a cyano group. G ² is a hydrogen atom;
M is an oxygen atom;
AC is —CH ₂ O—;
AD is selected from a direct bond and —C (═O) —; and AF or AF ^a is —C (═CH ₂ ) AG;
The compound according to claim 1 or 2. AD is a direct _{^{bond, - (CR AD R AD)}} m (O) (C = O) -, - (CH 2) 2 O-, and _{-AE (O) n (C =} O) p - is selected from The compound according to claim 11. AD is a direct _{^{bond, - (CR AD R AD)}} 2 O (C = O) -, - C (= O), - (CH 2) 2 O-, and
30. The compound of claim 29, selected from: 2. The compound of claim 1 selected from. A photolithographic composition comprising: (a) a photolithographic polymer; and (b) a compound according to any one of claims 1 to 31. A photoresist composition comprising (a) a photoresist polymer; and (b) a compound according to any one of claims 1 to 31.   34. A photoresist substrate coated with the photoresist composition of claim 33.   34. A method of manufacturing a photolithographic substrate comprising coating with the composition of claim 33.   A method of performing photolithography, comprising: (a) providing a substrate; (b) coating the substrate with the composition of claim 33; and (c) irradiating the coated substrate through a photomask. .   Performing photolithography on the substrate comprising: (a) providing a substrate; (b) coating the substrate with the composition of claim 33; and (c) irradiating the coated substrate through a photomask. how to.   37. The method of claim 36, wherein the irradiation is performed using electromagnetic radiation at a wavelength of 248 nm, 193 nm, 13.5 nm, or radiation from an electron or ion beam.